CN109749854A - A kind of technique by soap stock continuous production acidification oil and by-product sodium sulfate crystal - Google Patents
A kind of technique by soap stock continuous production acidification oil and by-product sodium sulfate crystal Download PDFInfo
- Publication number
- CN109749854A CN109749854A CN201910074339.9A CN201910074339A CN109749854A CN 109749854 A CN109749854 A CN 109749854A CN 201910074339 A CN201910074339 A CN 201910074339A CN 109749854 A CN109749854 A CN 109749854A
- Authority
- CN
- China
- Prior art keywords
- acid
- soap stock
- raw material
- reactor
- acidification oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000344 soap Substances 0.000 title claims abstract description 148
- 230000020477 pH reduction Effects 0.000 title claims abstract description 146
- 238000000034 method Methods 0.000 title claims abstract description 60
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 title claims abstract description 58
- 239000013078 crystal Substances 0.000 title claims abstract description 52
- 229910052938 sodium sulfate Inorganic materials 0.000 title claims abstract description 49
- 235000011152 sodium sulphate Nutrition 0.000 title claims abstract description 49
- 239000006227 byproduct Substances 0.000 title claims abstract description 39
- 238000010924 continuous production Methods 0.000 title claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 200
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 189
- 239000002253 acid Substances 0.000 claims abstract description 182
- 239000002994 raw material Substances 0.000 claims abstract description 128
- 239000000243 solution Substances 0.000 claims abstract description 66
- 239000000047 product Substances 0.000 claims abstract description 36
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011593 sulfur Substances 0.000 claims abstract description 14
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 14
- 239000000725 suspension Substances 0.000 claims abstract description 14
- 238000004062 sedimentation Methods 0.000 claims abstract description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 9
- 239000011734 sodium Substances 0.000 claims abstract description 9
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 5
- 238000003828 vacuum filtration Methods 0.000 claims abstract description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000000967 suction filtration Methods 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000000706 filtrate Substances 0.000 claims description 8
- 239000005864 Sulphur Substances 0.000 claims description 5
- 238000001514 detection method Methods 0.000 claims description 3
- 230000033228 biological regulation Effects 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000003921 oil Substances 0.000 description 166
- 235000019198 oils Nutrition 0.000 description 166
- 230000004087 circulation Effects 0.000 description 30
- 230000008569 process Effects 0.000 description 21
- 238000002156 mixing Methods 0.000 description 11
- 239000002351 wastewater Substances 0.000 description 10
- 238000003860 storage Methods 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 7
- 239000000498 cooling water Substances 0.000 description 6
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 5
- 230000003139 buffering effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000010902 straw Substances 0.000 description 4
- 244000068988 Glycine max Species 0.000 description 3
- 235000010469 Glycine max Nutrition 0.000 description 3
- 240000008042 Zea mays Species 0.000 description 3
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 3
- 235000005822 corn Nutrition 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000005755 formation reaction Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000011260 aqueous acid Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- CUGZTZSJLKHQGS-UHFFFAOYSA-M [Na+].[SH-].OS(O)(=O)=O Chemical compound [Na+].[SH-].OS(O)(=O)=O CUGZTZSJLKHQGS-UHFFFAOYSA-M 0.000 description 1
- 150000007513 acids Chemical group 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 238000009874 alkali refining Methods 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 238000010622 cold drawing Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 125000003473 lipid group Chemical group 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 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
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Provide a kind of technique by soap stock continuous production acidification oil and by-product sodium sulfate crystal, comprising: sulfuric acid and soap stock raw material a) are added into reactor, the two is made to be sufficiently mixed reaction；B) the upper layer oiliness reaction product in reactor is transferred to settler and carries out sedimentation layering；C) the upper layer acidification oil in settler is all sent to the feed pipe of soap stock raw material and soap stock raw material and is admitted to reactor together as reaction raw materials；Or a part is collected as product to acidification oil vessel, another part send to the feed pipe of soap stock raw material and soap stock raw material and is admitted to reactor together as reaction raw materials；D) lower layer's sulfur acid aqueous solution in settler is sent as a part of sulfuric acid raw material to reactor；E) suspension of lower layer's sulfur acid sodium crystal in reactor is transferred out of reactor, obtains byproduct sulfite crystal through vacuum filtration.The present invention realizes the continuous recycling of acid solution, and high conversion obtains acidification oil and obtains sodium sulfate crystal simultaneously.
Description
Technical field
The present invention generally belongs to soap stock processing technique field, produces acidification oil and by-product by soap stock more particularly to one kind
The technique of sour sodium crystal.
Background technique
Acidification oil refer to the byproduct soap stock produced to oil refining plant carry out acidification obtained oil.It is main
Want purposes: for cold drawing Silk Mill, steel plant, it may also be used for pharmaceutical factory, health care, feed factory, Bricks and Tiles Plant demould (isolation).Acid
Carburetion can be used for producing fatty acid, oleic acid, stearic acid, fatty acid methyl ester, plasticizer.
The production method of acidification oil mainly is acidified to obtain by soap stock at present.Soap stock is the by-product of oil and fat refining process
Object, wherein containing neutral oil (8-27%), soap (sodium soap) 30-40%, remaining be mainly water, there are also a small amount of free-fat
Acid, phosphatide and the substances such as lipides and pigment, total fatty acid content are up to 40-60%.Soap stock is mainly used for passing through acidification
Reaction production acidification oil, prior art mainly passes through acidification pool or acidification pot carries out acidification reaction, using intermittently operated, work
Skill is backward, soap stock conversion ratio is low, generates the big, severe operational environment of wastewater flow rate etc., is badly in need of a kind of high efficiency and environmentally friendly continuous life
Production. art.CN2012104969797 discloses a kind of method with preparation of biodiesel from by-product of alkali-refining of edible oils, is prepared and is acidified using alcoholysis method
Oil, process is complicated, it is big to generate wastewater flow rate；A kind of soap stock pot, CN201720969766.X disclosed in CN201721042152.3 are public
Soap stock disclosed in the soapstock treatment device and CN201520871336.5 opened refines oil pond, is all made of intermittently operated, and waste water generates
Amount is big, pollutes environment；107312626 A of CN discloses a kind of device with soap stock production acidification oil, although realizing continuous life
It produces, but still generates a large amount of waste acid water needs and be neutralized.And existing soap stock is prepared in the technique of acidification oil, acid
Utilization rate of liquid is only 50% or so.
Summary of the invention
It is an object of the invention to prepare for existing soap stock, the wastewater flow rate that acidification oil device and technique generate is big, Bu Nenglian
The defects such as continuous operation, soap stock conversion ratio be low, propose a kind of technique by soap stock continuous production acidification oil and by-product sodium sulfate crystal,
The technique realizes the continuous recycling of acid solution, and generation acid-bearing wastewater, high conversion obtain while obtaining acidification oil substantially
Byproduct sulfite, and the circulation of depickling acidification oil is combined, it reduces raw material reaction temperature, improve raw material reaction conversion
Rate.
In one aspect of the invention, a kind of work by soap stock continuous production acidification oil and by-product sodium sulfate crystal is provided
Skill, which is characterized in that it both makes to fill the following steps are included: the soap stock raw material after sulfuric acid and heating is added a), into reactor
Divide mixing, reaction；B), the upper layer oiliness reaction product in reactor is transferred to settler, oiliness reaction product is made to be sunk
Drop layering；C), the upper layer acidification oil after sedimentation layering in settler is transferred out of settler, is transferred out of the acidification oil quilt of settler
It all send to the feed pipe of soap stock raw material and soap stock raw material and is admitted to reactor together as reaction raw materials；Or be transferred out of it is heavy
The acidification oil a part for dropping device is collected as product to acidification oil vessel, and another part is sent to the feed pipe of soap stock raw material and soap
Foot raw material is admitted to reactor together as reaction raw materials；D), lower layer's sulfur-bearing after sedimentation layering in settler is acids molten
Liquid is transferred out of settler, and a part as sulfuric acid raw material is sent to reactor；E), the aqueous reactant of lower layer in reactor is arranged
It carries out vacuum filtration after the sodium crystal supersaturation of solution sulfur acid forms suspension in suction filtration tank to suction filtration tank out and obtains by-product
Product sodium sulfate crystal；Sulfuric acid and soap stock raw material continuous feed into reactor after heating in the step a)., above-mentioned steps
A) sulfuric acid and soap stock raw material continuous feed into reactor after heating in.
Upper layer acidification oil in the step c) of present invention process is mixed with soap stock raw material to be again introduced into reactor, is established
Acidification oil circulation loop, effect is first is that acidification oil mixes with soap stock raw material with residual temperature when reacting and improves soap stock raw material
Temperature soap stock raw material is reduced after mixing with soap stock raw material to reactor and charging second is that depickling has been carried out in acidification oil
The sour corrosion of pipeline；The step d) of technique is by returning the sulfur acid aqueous solution after sedimentation as a part of sulfuric acid raw material
It is back to reactor and establishes acid solution first circulation circuit, be recycled the sulfuric acid in settler lower layer water phase as raw material；
By soap stock raw material continuous feed all into reactor after sulfuric acid and heating, it is carried out continuously acidification reaction in reactor, instead
The acidification oil part that should be generated is stored as product, is partially used for reaction cycle process, the acid solution that do not react completely is through settling
After be recycled back in reactor and reacted again, the sodium sulfate crystal for reacting generation is discharged after reactor lower layer saturation, is passed through
Suction filtration obtains by-product sodium sulfate crystal；Throwing raw materials incessantly may be implemented in the process step of the invention, and realization is continuously given birth to
Produce acidification oil and by-product sodium sulfate crystal.
Further, further include in above-mentioned steps e), using the sulfur acid filtrate after vacuum filtration as the one of sulfuric acid raw material
It send to reactor part.
In the step e) of present invention process, reactor reaction lower layer aqueous product is outstanding containing sodium sulfate crystal and sulfuric acid
Supernatant liquid, the suspension after being filtered by vacuum and isolating sodium sulfate crystal is aqueous sulfuric acid, is returned it in reactor, is established
Acid solution second circulation circuit is recycled the acid solution in reactor lower layer water phase as raw material, in conjunction with settler above
Sulfuric acid in lower layer's water phase is recycled as raw material, is realized whole circulations of reaction process acid solution, is realized continuous production
Process is discharged without acid solution waste water.
Further, the sulfuric acid in above-mentioned steps a) be by with reactor feed mouth and the acid discharge being connected with sour container
Pump is admitted in reactor, and the concentrated sulfuric acid for being 98% with the mass percent stored in sour container is controllably sent by acid discharge pump
In reactor.
It is this to be respectively into the benefit of sour mode and high acid concentration: to be opened first is that can according to need real-time control acid discharge pump
It is dynamic, the sulfuric acid that reaction needs is sent into reactor；Second is that because of the dense of the sulfuric acid liquid being recycled back in reaction process in reactor
Spend lower, the concentrated sulfuric acid that mass percent is 98% be added thereto, can directly with the low-concentration sulfuric acid liquid that is recycled back to reactor
It is mixed to get the sulfuric acid solution that reaction needs concentration, reduce the water needed in advance with Sulphuric acid while does not need reaction process
Waste water discharge.
Further, the concentration of the sulfuric acid in above-mentioned steps a) in reactor is 30%-40% by mass percentage；
When initial reaction, the sulfuric acid in reactor pumps interval connection complex acid tank by acid discharge and water pot carries out concentration regulation；Reaction carries out
In the process, the sulfuric acid in reactor pumps connection complex acid tank by acid discharge and is controllably pumped into the matter stored in complex acid container to reactor
The concentrated sulfuric acid that amount percentage is 98% is regulated and controled.
The concentration of the sulfuric acid reacted in reactor with soap stock raw material be it is relatively-stationary, in 30%- by mass percentage
In 40% range.Reaction initial phase because through complex acid tank be pumped into be 98 mass percents be 98% the concentrated sulfuric acid, it is necessary to
Certain water is remixed by within the scope of its Concentration Modulation to 30%-40%, is just able to satisfy the condition of soap stock raw material acidification reaction；?
During reaction carries out, sulfuric acid is constantly consumed, and concentration gradually decreases, the sulfuric acid concentration that is back in the water phase of reactor is also low
In the concentration that reaction needs, at this moment controls acid discharge pump and is pumped into the concentrated sulfuric acid that the mass percent in complex acid tank is 98%, and it is anti-
The concentration that acid strength is needed to reaction in reactor is improved after answering the low concentration acid solution in device to be mixed.
Further, the heated device before being admitted to reactor of the soap stock raw material in above-mentioned steps a) is heated to 65-
75℃。
Soap stock raw material is preheated before entering the reactor, reduces the heating time that needs are reacted in reactor, is improved
Continuous production process.
It further, further include the step detected to the acid value for the acidification oil for being transferred out of settler in above-mentioned steps c)
It is rapid: when being transferred out of the acid value of acidification oil of settler and meeting predetermined value, to be transferred out of acidification oil a part of settler as producing
Product are collected to acidification oil vessel, and another part is sent to the feed pipe of soap stock raw material and soap stock raw material together as reaction raw materials quilt
It is sent into reactor.
It further, further include the step detected to the acid value for the acidification oil for being transferred out of settler in above-mentioned steps c)
Rapid: when being transferred out of the acid value of the acidification oil of settler and being unsatisfactory for predetermined value, the acidification oil for being transferred out of settler is all sent to soap
The feed pipe and soap stock raw material of foot raw material are admitted to reactor together as reaction raw materials.
For different soap stock raw materials, the acid value for the acidification oil as qualified products produced is different, according to
After soap stock raw material determines the acid value of qualified acidification oil, the acid value to the acidification oil for being transferred out of settler is detected, acidification is worked as
When the acid value of oil meets predetermined value requirement, the acidification oil for being transferred out of settler is split into two parts: a part is received as product
Collection to acidification oil vessel, another part send to the feed pipe of soap stock raw material and is admitted to soap stock raw material together as reaction raw materials
Reactor；When the acid value of acidification oil, which is unsatisfactory for predetermined value, to be required, oil is not taken, the acidification oil for being transferred out of settler is all sent
Feed pipe and soap stock raw material to soap stock raw material are admitted to reactor together as reaction raw materials.The behaviour of acidification oil acid value detection
Make with manual sampling can also be carried out by self-reacting device.
Further, further include in above-mentioned steps d) in settler sedimentation layering after lower layer's sulfur acid aqueous solution into
The step of row sulfuric acid content detects, when sulfuric acid content therein is lower than by mass 30%, control acid discharge pump will be in complex acid tank
98% concentrated sulfuric acid of mass percent be pumped into reactor.
Because of acid solution in reactor and soap stock raw material is admixed together is reacted, it is not easy to obtain sulfuric acid therein
Content, what the acid solution content back in settler lower layer water phase was answered is the content of first circulation acid solution, is contained with the acid solution in reactor
Measure it is almost the same, therefore, in settler sedimentation layering after lower layer's sulfur acid aqueous solution carry out sulfuric acid content detection, when it
In sulfuric acid content be lower than by mass 30% when, control acid discharge pump the dense sulphur of mass percent 98% is filled into reactor in time
Acid.
Further, in above-mentioned steps a) sulfuric acid and heating after soap stock raw material adding manner are as follows: first be added sulfuric acid extremely
Then soap stock raw material is continuously fed under sulfuric acid by the liquid level of sulfuric acid in 1/2 to 2/3 range of reaction kettle device internal height
Portion.
The Liquid level of aqueous sulfuric acid be in order to make the soap stock raw material of reactor bottom after sufficiently long floating-upward process,
Guarantee the contact and reaction time with acid solution.Similarly, soap stock raw material is continuously fed to the lower part of sulfuric acid, because soap stock raw material or containing
There is the mixing oil product density ratio aqueous sulfuric acid of acidification oil and soap stock raw material small, when charging makes foot raw material or contains acidification oil and soap
The mixing oil product of foot raw material is in the lower part of sulfuric acid, and such foot raw material or mixing oil product containing acidification oil and soap stock raw material will
It slowly floats, there is the process for being sufficiently mixed, reacting with sulfuric acid, make reaction more sufficiently, more thoroughly.
Further, the reaction temperature of the soap stock raw material in above-mentioned steps a) and sulfuric acid controls within the scope of 70-80 DEG C.
The reaction temperature of soap stock raw material and sulfuric acid is generally at 80 DEG C to 85 degree or so in the prior art because it is of the invention into
Material technique make to react soap stock raw material and sulfuric acid contact more sufficiently, react more thorough, make to be able to achieve at lower temperature under reacting
Reaction effect under higher temperature.
Further, above-mentioned soap stock raw material inlet amount hourly should be the 1/10-1/6 of acid solution total volume in reactor.
The inlet amount control of soap stock raw material can guarantee to have enough soap stock raw material and acid liquid reaction in reactor and not will lead to soap stock
Raw material is because excessive be settled down in settler without fully reacting.
Further, in above-mentioned steps d), lower layer's sulfur acid aqueous solution in settler after sedimentation layering passes through insertion
Self-straw draw mode be transferred out of settler.
Above-mentioned technique of the invention preferably passes through following dresses by soap stock continuous production acidification oil and by-product sodium sulfate crystal
Realization is set, a kind of device by soap stock continuous production acidification oil and by-product sodium sulfate crystal, it includes suction filtration tank, and reaction kettle sinks
Tank drops, and heater is acidified oil tank, raw material pump, head tank and acid cycle unit；The reaction kettle is raw material reactor, setting
There are acid solution feed inlet, soap stock feed inlet, top discharge mouth and lower discharge port；The head tank is former for storing reaction raw materials soap stock
Batch can is connected to heater through raw material pump, and the soap stock feed inlet connection of heater and reaction kettle will be sent after the heating of raw material soap stock
To reactor bottom；Top discharge mouth and the lower discharge port setting of the reaction kettle are in reaction kettle wall, and wherein the connection of top discharge mouth is heavy
Tank drops, so that acidification oil and part acid solution overflow are to settling tank, lower discharge port connects suction filtration tank, so that the suspension of reaction kettle bottom
It is expelled to suction filtration tank, suction filtration tank separates suspension and obtains sodium sulfate crystal；The acid cycle unit include self-priming surge tank and
Acid cycle pump, self-priming surge tank are connect through extending to the self-straw of sedimentation pot bottom with settling tank, another mouth of self-priming surge tank
Portion and acid cycle pump connect；Acid cycle pumps the acid solution feed inlet for being connected to reaction kettle, and the mixing that will settle pot bottom is molten
Liquid is sent into reaction kettle and is used as acid solution；The settling tank side wall upper part is provided with overflow port, described in the overflow port connection
It is acidified oil tank, to collect the acidification oil product on storage settling tank top.
As can be seen that passing through the design of acid cycle unit in apparatus of the present invention, solves and acidification oil work is prepared by soap stock
Acid-bearing wastewater emission problem in skill: after reaction raw materials carry out acidification reaction in reaction kettle, upper layer acidification oil and part acid solution
Enter settling tank through top discharge mouth to be settled, be layered, lower layer's acid solution in settling tank passes through and to settle tank connected self-priming slow
The self-straw for rushing tank, acid cycle pump under the action of be drawn out, then via self-priming surge tank and acid cycle pump into
Enter reaction kettle, thereby establishes first acid cycle and utilize circuit；Because relative to the acid content in reaction kettle bottom water phase
Speech, the content of lower layer's acid solution is much higher in settling tank, and what this acid cycle was solved using circuit is that height contains in preparation process
The recycling of amount acid solution is recycled, and finally to consume the acid solution in water phase, avoids waste acid water while improving acid solution utilization rate
Discharge, be not required to setting sour water in and device and sewage-treatment plant, reduce pollution of the technique to environment.
Further, above-mentioned apparatus further includes complex acid tank and acid discharge pump, and the complex acid tank and suction filtration tank are connected to acid discharge pump,
Acid discharge pumps the acid solution feed inlet for being connected to reaction kettle, and the suspension separating sodium sulfate that reactor bottom in suction filtration tank is discharged is brilliant
Filtrate after body is back to reaction kettle and adds acid solution to reaction kettle in real time during the reaction.
Complex acid tank and acid discharge pump and its connection type play two in apparatus of the present invention, first is that storing in complex acid tank
98% concentrated sulfuric acid is pumped from the acid solution feed inlet of reaction kettle through acid discharge and is pumped into reaction kettle, anti-according to the needs of reaction kettle
It should start to add sulfuric acid raw material in forward reaction kettle, and sulfuric acid liquid is replenished in time according to the Expenditure Levels of sulfuric acid during the reaction
Make the continuous uninterrupted progress of reaction into reaction kettle；Second is that suction filtration tank filters separating still bottom because suction filtration tank also connects acid discharge pump
The suspension of discharge, after sodium sulfate crystal is separated, filtrate contains a small amount of acid, and filtrate is pumped through acid discharge from the acid of reaction kettle
Liquid feed inlet is sent into reaction kettle and carries out secondary response again, this is that second acid cycle utilizes circuit.It is followed in conjunction with first acid solution
Ring utilizes circuit, and sulfuric acid utilization rate reaches 95% or more in apparatus of the present invention, be truly realized sulfuric acid dosage is few, acidification thoroughly,
No waste water generation, energy conservation and environmental protection.
Further, it is additionally provided with oily phase cycling element between the overflow port of above-mentioned settling tank and acidification oil tank, it is described
Oily phase cycling element includes circulation oil tank and oil circulating pump, and the overflow port connection circulation oil tank of settling tank recycles oil tank connection and follows
Ring oil pump, oil circulating pump are respectively connected to heater and acidification oil tank, so that the oil product part in circulation oil tank enters acidification oil
Tank, the heated device in part enter in reaction kettle.
The acidification oil flowed out through settling tank overflow port is obtained via the acidification reaction in reaction kettle, so temperature with higher
Degree, it and reaction raw materials soap stock enter heater together, on the one hand can preheat cold soap stock raw material, on the other hand use acidification oil
To drive soap stock, flowing can be to avoid soap stock to the acid corrosion inside device, because of acidification oil depickling in a device together.
Therefore, it is followed by the acidification oil for being recycled back to the heated device of a part of acidification oil in reaction kettle from reaction kettle soap stock material inlet
Ring can save the energy of heater heating consumption of raw materials, mitigate damage of the raw material to equipment, and keep the acidification in reaction kettle anti-
It should be easier to carry out.
Also further, above-mentioned soap stock feed inlet is arranged in reaction kettle upper end, is connected with the charging for extending to reaction kettle lower part
Pipe, so that the oiliness reaction raw materials for entering reaction kettle through soap stock feed inlet are admitted to reaction kettle lower part.
Because the mixing oil product density ratio aqueous sulfuric acid containing acidification oil and soap stock raw material is small, acid solution can be carried out
The optimal setting of feed inlet and soap stock feed inlet and feeding manner makes to make to mix the lower part that oil product is in sulfuric acid when charging, in this way
Mixing oil product will slowly float, and have the process for being sufficiently mixed, reacting with sulfuric acid.The setting of other oral areas of combined reaction kettle, is adopted
Take reaction kettle upper end is arranged in soap stock feed inlet, the setting of feed pipe by extending to reaction kettle lower part be opposite optimization side
Mixing oil product can be sent straight to reaction kettle sulfuric acid liquid lower part, carry out it during opposite sulfuric acid liquid floats by case
Sufficient acidification reaction.
Further, it is provided with distributor in aforesaid reaction vessel, in the raw material uphill process for making reactor bottom
Even distribution, comes into full contact with acid solution.
The mixing oil product of soap stock and acidification oil, via distributor, on the one hand can make miscella product upper in floating-upward process
It rises and is evenly distributed on cross section, avoid being formed in sulfuric acid and concentrate upper up-flow and blank area, reacting mixing oil product really with sulfuric acid
Kettle uniformly contacts in space；Second is that the rate of climb of oil product is reduced via distributor, when extending contact of the oil product with sulfuric acid
Between, to ensure that the abundant progress of acidification reaction on room and time, reaction conversion ratio is made to reach 90% or more, it is really real
Plant soap stock is showed and sulfuric acid sufficiently reacts.
Also further, above-mentioned apparatus further includes pumped vacuum systems, negative pressure storage tank, the pumped vacuum systems connection negative pressure storage
Tank, the negative pressure storage tank are connected to suction filtration tank, for providing the vacuum environment by buffering for suction filtration tank preferably to filter point
Sodium sulfate crystal and water phase are obtained from the suspension being discharged from reaction kettle bottom.Pumped vacuum systems, which is used to provide for suction filtration tank, filters institute
The vacuum environment needed, negative pressure storage tank its buffering and over effect between pumped vacuum systems and suction filtration tank, by negative pressure of vacuum environment
Variation to filter effect and efficiency influence minimize.
Also further, above-mentioned apparatus further includes reaction kettle temperature conditioning unit, the reaction kettle temperature conditioning unit include vapour source,
Cooling water source and pipeline or the channel that reaction kettle wall periphery is set, so that vapour source, cooling water source alternately access the pipeline
Or channel, achieve the purpose that control raw material reaction temperature in reaction kettle.
The suitable temperature of acidification reaction is at 80 DEG C or so in reaction kettle, but acidification reaction starts rear reaction process itself and can produce
Heat amount, it is possible to will lead to reactor temperature and further increase even mixed liquor boiling, therefore use steam and cooling water
The mode for alternately controlling reactor temperature heats reaction kettle with hot steam in reaction beginning or fill process, makes material temperature
Degree increases, and starts acidification reaction and to prevent reactor temperature excessively high, is intermittently passed through cooling water during the reaction and is dropped
Temperature processing, controls reaction temperature always within a predetermined range.
Following process can will be divided by the technique of soap stock continuous production acidification oil and by-product sodium sulfate crystal:
(1) reaction step: aqueous sulfuric acid is added into reaction kettle, and (in preferred embodiment, complex acid tank prepares the sulphur of 20-40%
Aqueous acid is pumped into reaction kettle by acid discharge, is maintained at liquid level in 1/2 to 2/3 range of kettle cavity heights), head tank
Interior soap stock is pumped by raw material, and (preferred embodiment is within the scope of 65-75 DEG C) enters instead afterwards after being heated by the heaters certain temperature
The soap stock feed inlet for answering kettle enters reactor bottom by feed pipe (soap stock inlet amount is 1.0-2.0 ton/hours)；Due to soap
Foot density ratio water is low, during slowly floating to upper layer from bottom, comes into full contact with and reacts with acid solution, upper layer acid in reaction kettle
Carburetion and the reacted kettle top discharge mouth of part acid solution, which enter in settling tank, to be settled；Upper layer acidification oil reaches overflow in settling tank
Overflow to circulating tank, a part of acidification oil is sent after oil circulating pump pumping is mixed and heated with raw material soap stock to reaction kettle after mouthful
Soap stock feed inlet, establishes acidification oil forced circulation, and the mode that the acid solution of settling tank lower layer enters through self-priming enters self-priming buffering
Tank, and the acid solution feed inlet for being pumped into reaction kettle through acid cycle is recycled, and realizes that acid solution is applied repeatedly, is improved acid solution and is utilized
Rate is to 95% or more.
(2) product separation circulation: the acidification oil by upper layer in reaction kettle with a small amount of sodium soap and metabisulfite solution is certainly
Settling tank is flowed to, metabisulfite solution density is deposited to the bottom of settling tank greater than acidification oil, and acidification oil oil reservoir is in upper layer, acidification
Oil flows into circulation oil tank from overflow pipe, to be continued by oil circulating pump and return reaction kettle after raw material soap stock Hybrid Heating
Acidification reaction, metabisulfite solution enter self-sucking pot by self-priming effect, return to reaction kettle by acid pump, establish sulphur respectively in this way
Acid sodium solution circulation is mutually recycled with oil, and part acidic oil, which is pumped to acidification oil tank, becomes product.
(3) by-product separates: with the progress of acidification reaction in reaction kettle, sulfuric acid participates in reaction and generates sodium sulphate, sulphur
Sodium sulfate crystal is precipitated after sour sodium saturation, the blow-off valve discharge part for opening reaction kettle lower discharge port contains the outstanding of sulfate crystal
Turbid isolates sodium sulfate crystal through suction filtration tank suction filtration, and sodium sulphate is obtained as byproduct, directly outer can sell；It filters and divides
Sulfur acid and sodium sulphate filtrate liquid from after are recycled again through 15 return reaction kettle 4 of acid discharge pump.
(4) acid solution applies supplement: with the progress of acidification reaction, sulfuric acid content is gradually decreased in reaction kettle, needs to monitor
Sulfuric acid content simultaneously fills into sulfuric acid in time, maintains the content of sulfuric acid in reaction kettle, makes acidification reaction continue to carry out, 98% in complex acid tank
The sulfuric acid solution of concentration is added to the acid solution feed inlet of reaction kettle by acid discharge pump, keeps the sulphur in reaction kettle in aqueous sulfuric acid
Acid content is within the scope of 30-40% by mass.
In present invention process, soap stock continuous feed, acidification oil continuous discharge may be implemented soap stock and generate the continuous of acidification oil
Production, while acid solution applies the discharge for avoiding waste acid water, is not required in setting sour water reduce with device and sewage-treatment plant
Pollution of the technique to environment.
Technique of the invention passes through sulfuric acid and soap in sulfuric acid solution recycled, the reaction of acidification oil forced circulation, reaction kettle
The modes such as the reaction was continued and recycles in acid solution return kettle after foot feeding process, sodium sulfate salt suction filtration crystallization are precipitated, convert reaction
Rate reaches 90% or more, and sulfuric acid utilization rate reaches 95% or more, be truly realized plant soap stock and sulfuric acid sufficiently react, sulfuric acid use
Amount is less, acidification is thorough, generates without waste water, energy conservation and environmental protection.
Detailed description of the invention
From the detailed description with reference to the accompanying drawing to the embodiment of the present invention, these and/or other aspects of the invention and
Advantage will become clearer and be easier to understand, in which:
Fig. 1 is that the present invention is completed in the embodiment of the present invention by soap stock continuous production acidification oil and by-product sodium sulfate crystal technique
The apparatus structure schematic diagram used；
Wherein: 1- pumped vacuum systems, 2- negative pressure storage tank, 3- suction filtration tank, 4- reaction kettle, 5- settling tank, 6- self-priming surge tank,
7- recycles oil tank, and 8- acid cycle pumps, 9- heater, 10- oil circulating pump, and 11- is acidified oil tank, and 12- raw material pumps, 13- head tank,
14- complex acid tank, 15- acid discharge pump.
Specific embodiment
In order to make those skilled in the art more fully understand the present invention, with reference to the accompanying drawings and detailed description to this hair
It is bright to be described in further detail.
Embodiment 1
A kind of device by soap stock continuous production acidification oil and by-product sodium sulfate crystal, as shown in Figure 1, it includes vacuumizing
System 1, negative pressure storage tank 2, suction filtration tank 3, reaction kettle 4, settling tank 5, surge tank 6, circulation oil tank 7, acid cycle pump 8, heater
9, oil circulating pump 10, acidification oil tank 11, raw material pump 12, head tank 13, complex acid tank 14, acid discharge pump 15；Reaction kettle 4 is raw material reaction
Device is provided with acid solution feed inlet, soap stock feed inlet, top discharge mouth and lower discharge port；Head tank 13 is for storing reaction raw materials soap
Foot, head tank 13 are connected to heater 9 through raw material pump 12, and heater 9 is connect with the soap stock feed inlet of reaction kettle 4, by raw material
It send after soap stock heating to 4 bottom of reaction kettle；The top discharge mouth and lower discharge port of reaction kettle 4 are arranged in 4 wall of reaction kettle, wherein above going out
Material mouth connects settling tank 5, so that acidification oil and part acid solution overflow are to settling tank 5, lower discharge port connects suction filtration tank 3, so that instead
The suspension of 4 bottom of kettle is answered to be expelled to suction filtration tank 3, suction filtration tank 3 separates suspension and obtains sodium sulfate crystal and filtrate；Self-priming buffering
Tank 6 is connect through extending to the self-straw of 5 bottom of settling tank with settling tank 5, another oral area and the acid cycle pump 8 of self-priming surge tank 6
Connection, acid cycle pump 8 are connected to the acid solution feed inlet of reaction kettle 4, and the mixed solution of 5 bottom of settling tank is sent into reaction kettle
It is used in 4 as acid solution；5 side wall upper part of settling tank is provided with overflow port, overflow port connection circulation oil tank 7, and circulation oil tank 7 connects
Oil circulating pump 10, oil circulating pump 10 are respectively connected to heater 9 and acidification oil tank 11, so that the oil product part in circulation oil tank 7
Into acidification oil tank 11, the heated device 9 in part enters in reaction kettle 4；Complex acid tank 14 and suction filtration tank 3 are connected to acid discharge pump 15, row
Acid pump 15 is connected to the acid solution feed inlet of reaction kettle 4, by the sodium sulfate crystal suspension separating sodium sulfate crystal in suction filtration tank 3
Filtrate afterwards is back to reaction kettle 4 and adds acid solution to reaction kettle 4 in real time during the reaction；In preferred embodiment, soap
Foot feed inlet is arranged in 4 upper end of reaction kettle, the feed pipe for extending to 4 lower part of reaction kettle is connected with, so as to enter through soap stock feed inlet
The oiliness reaction raw materials of reaction kettle are admitted to reaction kettle lower part, in a kettle because density ratio aqueous sulfuric acid density is small and
It floats, to come into full contact with aqueous sulfuric acid, preferred mode is that distributor is provided in reaction kettle 4, is further made
It is spatially and temporally above contacted with acid solution in the soap stock raw material uphill process of 4 lower part of reaction kettle more abundant；Pumped vacuum systems 1 connects
Negative pressure storage tank 2 is connect, negative pressure storage tank 2 is connected to suction filtration tank 3, for providing the vacuum environment by buffering for suction filtration tank 3 with more preferable
Ground filters separation and obtains sodium sulfate crystal and water phase from the suspension that 4 bottom of reaction kettle is discharged；The temperature control of reaction kettle is using steaming
Vapour source, cooling water source and pipeline or channel that reaction kettle wall periphery is set, so that described in the alternating access of vapour source, cooling water source
Pipeline or channel achieve the purpose that control raw material reaction temperature in reaction kettle 4.
Embodiment 2
A kind of technique by soap stock continuous production acidification oil and by-product sodium sulfate crystal, it utilizes the device of embodiment 1, work
Skill process is as follows:
A) aqueous sulfuric acid is added in reaction kettle (4)；Soap stock in head tank (13) enters heating by raw material pump (12)
Device (9) is entered reaction kettle (4) bottom through soap stock feed inlet after heater (9) heating；Soap stock from reaction kettle (4) bottom floating to
It comes into full contact with and reacts with acid solution during upper layer, the interior upper layer acidification oil of reaction kettle (4) and the reacted kettle of part acid solution (4)
Top discharge mouth enters settling tank (5) and is settled；
B) overflow to acidification oil fills (11) or single through oily mutually circulation after settling tank (5) upper layer acidification oil reaches overflow port position
A first branch point enters the acidification oil filling heated device of (11) another part (9) and is back to reaction kettle (4)；
C) acid solution of settling tank (5) lower layer is sent to reaction kettle through the acid solution feed inlet of acid cycle unit and reaction kettle
(4)；
D) the reacted kettle of the suspension containing sulfate crystal (4) lower discharge port of reaction kettle (4) bottom is expelled to suction filtration
Tank (3), filters isolated sodium sulfate crystal.
In the present embodiment, device mainly realizes following technique purpose:
(1) acidification reaction: soap stock and acid solution come into full contact with and react in reaction kettle 4, and acid cycle is applied, and oil mutually recycles anti-
Qualified acidification oil product should be obtained, realizes continuous feed and continuous discharge.
(2) product separates: the fatty acid oil reservoir by upper layer in reaction kettle 4 with a small amount of sodium soap and metabisulfite solution is certainly
Settling tank 5 is flowed to, metabisulfite solution is deposited to tank bottom, and fatty acid oil reservoir establishes metabisulfite solution circulation and oil on upper layer respectively
It mutually recycles, after reaction kettle exports acid value qualification, qualified acidification oil is pumped to acidification oil tank 11.
Embodiment 3
A kind of technique by soybean soap stock raw material continuous production acidification oil and by-product sodium sulfate crystal, it utilizes embodiment 1
Device, steps are as follows for concrete technology flow process: 35% aqueous sulfuric acid, the soybean soap stock in head tank 13 being added in reaction kettle 4
Raw material is pumped after being heated to 50 DEG C by raw material, according to 2 tons per hour of processing capacity, is entered after being heated to 70 DEG C by heater 9
In reaction kettle 4.Acidification reaction occurs in reaction kettle 4.Oil reservoir reacted kettle upper end outlet in top enters settling tank 5.Settling tank 5
For the overflow of upper-layer fat acid to circulation oil tank 7, the heated device 9 of part acidic oil recycled in oil tank 7 mixes oil product with raw material formation
Reaction kettle 4 is returned, oil product circulation is established, the mixed solution of lower layer's deposition pumps 8 sucking self-priming surge tanks 6 with acid cycle, then
It is pumped into the circulation of reaction kettle 4.Send the part acidic oil pump recycled in oil tank 7 to acidification oil tank 11, yield about 1.7 tons of left sides per hour
It is right.Strong acid is replenished in time when the sulfuric acid concentration of 5 lower layer of settling tank is lower than 30% and maintains acid content in reaction kettle.4 kettle of reaction kettle
It is precipitated crystal after the sodium sulphate saturation that bottom generates, drains into suction filtration tank and recrystallized, as byproduct, yield is per hour 0.42
Ton or so.The technique can continuous feed and continuous discharge, realize soap stock continuous production acidification oil, product acidification oil acid value reaches
150-160mgKOH/g, acidification reaction high conversion rate is up to 92%.
Embodiment 4
A kind of technique by corn soap stock raw material continuous production acidification oil and by-product sodium sulfate crystal, it utilizes embodiment 1
Device, steps are as follows for concrete technology flow process: 38% aqueous sulfuric acid, the corn soap stock in head tank 13 being added in reaction kettle 4
Raw material is pumped after being heated to 50 DEG C by raw material, according to 1.5 tons per hour of processing capacity, is heated by the heaters to entering after 75 DEG C
In reaction kettle 4.Acidification reaction occurs in reaction kettle 4.Oil reservoir reacted kettle upper end outlet in top enters settling tank 5.Settling tank 5
For the overflow of upper-layer fat acid to circulation oil tank 7, the heated device 9 of part acidic oil recycled in oil tank 7 mixes oil product with raw material formation
Reaction kettle 4 is returned, oil product circulation is established, the mixed solution of lower layer's deposition pumps 8 sucking self-priming surge tanks 6 with acid cycle, then
It is pumped into the circulation of reaction kettle 4.Part acidic oil pump in circulation oil tank 7 send acidification oil tank 11, yield about 1.3 tons of left sides per hour
It is right.Strong acid is replenished in time when the sulfuric acid concentration of 5 lower layer of settling tank is lower than 30% and maintains acid content in reaction kettle.4 kettle of reaction kettle
It is precipitated crystal after the sodium sulphate saturation that bottom generates, drains into suction filtration tank and recrystallized, as byproduct, yield is per hour 0.32
Ton or so.The technique can continuous feed and continuous discharge, realize soap stock continuous production acidification oil, corn acidification oil acid value reaches
120-130mgKOH/g, acidification reaction high conversion rate is up to 93%.
Embodiment 5
A kind of technique by corn soap stock raw material continuous production acidification oil and by-product sodium sulfate crystal, it utilizes embodiment 1
Device, be added 35% sodium sulphate aqueous acid in reaction kettle 4, the soybean soap stock raw material in head tank 13, after being heated to 50 DEG C,
It is pumped by raw material, according to 2 tons per hour of processing capacity, is heated by the heaters to after 70 DEG C and enters in reaction kettle 4.In reaction kettle 4
Interior generation acidification reaction.Oil reservoir reacted kettle upper end outlet in top enters settling tank 5.5 upper-layer fat acid overflow of settling tank is to following
Ring oil tank 7, the heated device 9 of part acidic oil recycled in oil tank 7 mix oil product return reaction kettle 4 with raw material formation, establish oil
The mixed solution of product circulation, lower layer's deposition pumps 8 sucking self-priming surge tanks 6 with acid cycle, is then pumped into the circulation of reaction kettle 4.
Part acidic oil pump in circulation oil tank 7, which is sent, is acidified oil tank 11, and about per hour 1.71 tons or so of yield.When 5 lower layer of settling tank
Sulfuric acid concentration is replenished in time sodium sulphate acid and maintains acid content in reaction kettle when being lower than 30%.The sodium sulphate that 4 bottom of reaction kettle generates
It is precipitated crystal after saturation, drains into suction filtration tank and recrystallized, as byproduct, yield is 0.42 ton or so per hour.The technique
Can continuous feed and continuous discharge, realize soap stock continuous production acidification oil.150-160mgKOH/g, acidification reaction high conversion rate
Up to 92%.
Various embodiments of the present invention are described above, above description is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.Without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes are obvious for the those of ordinary skill in art field.Therefore, protection scope of the present invention is answered
This is subject to the protection scope in claims.
Claims (10)
1. a kind of technique by soap stock continuous production acidification oil and by-product sodium sulfate crystal, which is characterized in that it includes following step
It is rapid:
A), the soap stock raw material after sulfuric acid and heating are added into reactor, makes the two be sufficiently mixed, react；
B), the upper layer oiliness reaction product in reactor is transferred to settler, oiliness reaction product is made to carry out sedimentation layering；
C), the upper layer acidification oil after sedimentation layering in settler is transferred out of settler, the acidification oil for being transferred out of settler is complete
It send to the feed pipe of soap stock raw material and soap stock raw material and is admitted to reactor together as reaction raw materials in portion；Or it is transferred out of sedimentation
Acidification oil a part of device is collected as product to acidification oil vessel, and another part is sent to the feed pipe of soap stock raw material and soap stock
Raw material is admitted to reactor together as reaction raw materials；
D), lower layer's sulfur acid aqueous solution after sedimentation layering in settler is transferred out of settler, one as sulfuric acid raw material
It send to reactor part；
E), the aqueous reactant of lower layer in reactor is expelled to suction filtration tank, when solution sulfur acid sodium crystal is satiated in suction filtration tank
After forming suspension, carries out vacuum filtration and obtain byproduct sulfite crystal；
Sulfuric acid and soap stock raw material continuous feed into reactor after heating in the step a).
2. as described in claim 1 by the technique of soap stock continuous production acidification oil and by-product sodium sulfate crystal, which is characterized in that
It further include sending the sulfur acid filtrate after vacuum filtration to reactor as a part of sulfuric acid raw material in the step e).
3. the technique of soap stock continuous production acidification oil and by-product sodium sulfate crystal as claimed in claim 2, which is characterized in that institute
Stating the sulfuric acid in step a) is admitted in reactor by the acid discharge pump being connected with reactor feed mouth and with sour container,
The concentrated sulfuric acid for being 98% with the mass percent stored in sour container is pumped in controllably feeding reactor by acid discharge.
4. the technique of soap stock continuous production acidification oil and by-product sodium sulfate crystal as claimed in claim 3, which is characterized in that described
The concentration of sulfuric acid in step a) in reactor is 30%-40% by mass percentage；Sulphur when initial reaction, in reactor
Acid pumps interval connection complex acid tank by acid discharge and water pot carries out concentration regulation；During reaction carries out, the sulfuric acid in reactor is logical
It crosses acid discharge pump connection complex acid tank and is controllably pumped into the concentrated sulfuric acid that the mass percent stored in complex acid container is 98% to reactor
Regulated and controled.
5. the technique of soap stock continuous production acidification oil and by-product sodium sulfate crystal as claimed in claim 2, which is characterized in that institute
It states the heated device before being admitted to reactor of the soap stock raw material in step a) and is heated to 65-75 DEG C.
6. the technique of soap stock continuous production acidification oil and by-product sodium sulfate crystal as claimed in claim 2, which is characterized in that institute
It states in step c), further includes the steps that the acid value to the acidification oil for being transferred out of settler detects: when being transferred out of settler
When the acid value of acidification oil meets predetermined value, the acidification oil a part for being transferred out of settler is collected as product to acidification oil vessel,
Another part send to the feed pipe of soap stock raw material and soap stock raw material and is admitted to reactor together as reaction raw materials.
7. the technique of soap stock continuous production acidification oil and by-product sodium sulfate crystal as claimed in claim 2, which is characterized in that institute
It states in step c), further includes the steps that the acid value to the acidification oil for being transferred out of settler detects: being transferred out of the acid of settler
When the acid value of carburetion is unsatisfactory for predetermined value, the acidification oil for being transferred out of settler is all sent to the feed pipe of soap stock raw material and soap
Foot raw material is admitted to reactor together as reaction raw materials.
8. the technique of soap stock continuous production acidification oil and by-product sodium sulfate crystal as described in claim 3 or 4, feature exist
In, further include in the step d) in settler sedimentation layering after lower layer's sulfur acid aqueous solution carry out sulfuric acid content detection
The step of, when sulfuric acid content therein is lower than by mass 30%, control acid discharge is pumped the mass percent in complex acid tank
98% concentrated sulfuric acid is pumped into reactor.
9. the technique of soap stock continuous production acidification oil and by-product sodium sulfate crystal as claimed in claim 2, which is characterized in that institute
The adding manner of soap stock raw material after stating sulfuric acid in step a) and heating are as follows: first addition sulfuric acid is to its liquid level inside reaction kettle device
In 1/2 to 2/3 range of height, then soap stock raw material is continuously fed to the lower part of sulfuric acid solution.
10. the technique of soap stock continuous production acidification oil and by-product sodium sulfate crystal as claimed in claim 9, which is characterized in that
The reaction temperature of soap stock raw material and sulfuric acid in the step a) controls within the scope of 70-80 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910074339.9A CN109749854A (en) | 2019-01-25 | 2019-01-25 | A kind of technique by soap stock continuous production acidification oil and by-product sodium sulfate crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910074339.9A CN109749854A (en) | 2019-01-25 | 2019-01-25 | A kind of technique by soap stock continuous production acidification oil and by-product sodium sulfate crystal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109749854A true CN109749854A (en) | 2019-05-14 |
Family
ID=66404899
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910074339.9A Pending CN109749854A (en) | 2019-01-25 | 2019-01-25 | A kind of technique by soap stock continuous production acidification oil and by-product sodium sulfate crystal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109749854A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB658458A (en) * | 1948-12-18 | 1951-10-10 | Standard Oil Dev Co | Improvements in or relating to the recovery of fatty acids from dilute aqueous solutions |
| US20010049452A1 (en) * | 2000-03-24 | 2001-12-06 | Reaney Martin J. | Method for soapstock acidulation |
| CN102965200A (en) * | 2012-11-29 | 2013-03-13 | 青岛福瑞斯生物能源科技开发有限公司 | Method for preparing biodiesel from nigre |
| CN103409242A (en) * | 2012-11-09 | 2013-11-27 | 广州市南洋国际工程技术服务公司 | Recycling process for alkali refining by-product, namely soapstock in refining vegetable oil and reactor |
| CN105754724A (en) * | 2016-03-07 | 2016-07-13 | 九江力山环保科技有限公司 | Method for direct conversion of plant soapstock into fatty acid |
| CN207130232U (en) * | 2017-08-08 | 2018-03-23 | 嘉里粮油（营口）有限公司 | A kind of soap stock acidification oil retort and oily-water seperating equipment |
-
2019
- 2019-01-25 CN CN201910074339.9A patent/CN109749854A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB658458A (en) * | 1948-12-18 | 1951-10-10 | Standard Oil Dev Co | Improvements in or relating to the recovery of fatty acids from dilute aqueous solutions |
| US20010049452A1 (en) * | 2000-03-24 | 2001-12-06 | Reaney Martin J. | Method for soapstock acidulation |
| CN103409242A (en) * | 2012-11-09 | 2013-11-27 | 广州市南洋国际工程技术服务公司 | Recycling process for alkali refining by-product, namely soapstock in refining vegetable oil and reactor |
| CN102965200A (en) * | 2012-11-29 | 2013-03-13 | 青岛福瑞斯生物能源科技开发有限公司 | Method for preparing biodiesel from nigre |
| CN105754724A (en) * | 2016-03-07 | 2016-07-13 | 九江力山环保科技有限公司 | Method for direct conversion of plant soapstock into fatty acid |
| CN207130232U (en) * | 2017-08-08 | 2018-03-23 | 嘉里粮油（营口）有限公司 | A kind of soap stock acidification oil retort and oily-water seperating equipment |
Non-Patent Citations (5)
| Title |
|---|
| （美）惠（HUI，Y.H.）主编，徐生庚，等译: "《贝雷.第4卷：油脂化学与工艺学》", 30 June 2001 * |
| 彭渝翔: "《植物油厂综合利用》", 31 October 1996, 中国商业出版社 * |
| 金昌海: "《粮油饲料加工与储检》", 30 September 2016, 中国轻工业出版社 * |
| 韩长日，等: "《化工小商品生产法（第17集）》", 31 August 1996, 湖南科学技术出版社 * |
| 饶华俊，等: "鳀鱼油皂脚的酸化工艺优化", 《食品与发酵工业》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102492546B (en) | Rice bran oil refinement and byproduct production method | |
| CN209428133U (en) | A kind of crude product sodium pyrophosphate purification produces the device of sodium ascorbyl phosphate and sodium chloride | |
| CN207856912U (en) | A kind of lithium battery tertiary precursor synthesis apparatus system | |
| CN201334477Y (en) | Mechanical stirring and circulation combined fermentation reactor | |
| CN206736052U (en) | A kind of integrated treatment reactor of sludge wet oxidation | |
| CN114259961A (en) | System and method for improving capacity of lithium battery anode material precursor and regulating and controlling particle size distribution of precursor | |
| CN102173978B (en) | Dihydromyrcenol fixed bed hydration continuous production method | |
| CN109749853A (en) | A kind of device by soap stock continuous production acidification oil and by-product sodium sulfate crystal | |
| CN109749854A (en) | A kind of technique by soap stock continuous production acidification oil and by-product sodium sulfate crystal | |
| CN108698871A (en) | Device and method for biological treatment debirs and sewage | |
| CN210560330U (en) | Device for continuously producing acidified oil and byproduct sodium sulfate crystals from soapstock | |
| CN102676703A (en) | Method and equipment for clarifying cane juice by combining air floatation purification and thermal floatation purification | |
| CN205803463U (en) | A kind of pre-vaccination anaerobic ferment devices | |
| CN201330250Y (en) | Gas lift type circulating compound fermenting reactor | |
| CN202671225U (en) | System for producing liquid polyaluminium chloride | |
| CN205933523U (en) | High salt organic wastewater of EDTA and resources recovery system | |
| CN202595006U (en) | Neutralization and water washing continuous device for citric ester | |
| CN107304403A (en) | A kind of new batch-type anaerobic reaction technique | |
| CN212954949U (en) | Chlorobutane continuous production device | |
| CN207259466U (en) | Crude oil alkali refining mechanism | |
| CN201439031U (en) | High-density clarification tank | |
| CN102649748A (en) | Neutralization and water washing continuation device of citrate | |
| CN208948920U (en) | A kind of settler of environmental protection treatment sewage | |
| CN112195068A (en) | Process for producing fatty acid by taking soapstock as raw material and production equipment thereof | |
| CN207130232U (en) | A kind of soap stock acidification oil retort and oily-water seperating equipment |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Jin Hui Inventor after: Tang Qiang Inventor after: Jiang Shunbo Inventor after: Yang Jinyan Inventor after: Liu Ying Inventor before: Jin Hui Inventor before: Tang Qiang Inventor before: Jiang Shunbo |
|
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190514 |