CN1087029C - Production of fatty acid methyl esters and soap therefrom - Google Patents
Production of fatty acid methyl esters and soap therefrom Download PDFInfo
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- CN1087029C CN1087029C CN 95197987 CN95197987A CN1087029C CN 1087029 C CN1087029 C CN 1087029C CN 95197987 CN95197987 CN 95197987 CN 95197987 A CN95197987 A CN 95197987A CN 1087029 C CN1087029 C CN 1087029C
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Abstract
The present invention relates to a method for preparing esters and water soluble soaps through intensive mixing by using a device disclosed in the specification, which comprises the following steps: reacting fat and oil with methanol containing alkali as a catalyst; then, removing generated glycerol to prepare the esters. The esters are saponified with the alkali and additional amount of methanol to generate soaps.
Description
Invention field
The present invention relates to produce apace by natural fat and oily less energy-consumption the method for soap by fatty acid methyl ester.More particularly, the present invention relates to utilize sufficient stirring method, in this method, fat and oil at first are processed into fatty acid methyl ester, generate fatty acid soaps through saponification afterwards.
Background of invention
The path that is produced soap by methyl esters comprises: at first produce fatty acid methyl ester (transesterify) by fat and oil, methyl esters obtains soap through saponification subsequently, reclaims the methyl alcohol that obtains simultaneously, and its reaction formula is as follows:
In the US of Bradshaw and Meuly patent 2271619, described with low-molecular-weight alcohol such as methyl alcohol or ethanol and replaced glycerine in the fat.It is said that this method can be directly produces methyl esters or ethyl ester and do not disturb hydrolysis from fat, and can carry out at low temperatures.Although reaction can be carried out in uncovered jar of being made by plain carbon stool, the preferred container that uses sealing.Fat must be totally, drying and be essentially neutrality.Fat is heated to 80 ℃ (176 °F), and to wherein adding the industrial anhydrous methanol (99.7%) that is dissolved with 0.1-0.5% sodium hydroxide or potassium hydroxide.Though think that the consumption of alcohol can reduce to 1.2 times of theoretical value if adopt three stepping line operates, the consumption of the alcohol of recommending is 1.6 times of the required theoretical value of reaction.The consumption of alcohol is higher than 1.75 times of greatly accelerated reactions of theoretical value, and thinks that it disturbs glycerine gravity separation subsequently.
This of Bradshaw piece patent expectation uses methyl esters to produce anhydrous soap by continuous processing.It is said that ester can come saponification with caustic soda or Ke Xingjia at low temperatures, and methyl alcohol can reuse.The methyl esters of lipid acid or ethyl ester are mobile, and be relatively stable, non-corrosive lower boiling derivative; And in some operation, they are preferably with release fat acid.Methyl esters preferably because its production cost is low, has pyrolysis stability preferably than ethyl ester in technological process such as the fractionation process.
Also according to reports, have only fat to be almost neutrality and reaction mixture when anhydrous basically, the alcoholysis method of base catalysis just can be successful fully.If can not satisfy above-mentioned arbitrary condition, will cause that soap forms, thereby cause the loss of basicity and the generation of gel structure.The generation of gel can stop and postpone separating and sedimentation of glycerine.
Coming fatty acid methyl ester is carried out saponification with alkali is known to produce soap.Its production unit can have been bought with the Lion company and the Italian Ballestra company of for example Japan.Produced in the currently known methods of soap by fatty acid methyl ester, methyl esters at first contains the soap body (soap mass) of water and methyl alcohol with alkali reaction production.In following step, remove excessive water and methyl alcohol.There are several processing steps to realize this step.For example, soap body is positioned on the going barrel with film can removes methyl alcohol.Thereby soap body is converted to soap flakes, can be further dry to it by a baking oven with soap flakes.
Yet, produce soap by these methods of prior art by the methyl esters saponification and have following shortcoming:
1. because all reactions are at room temperature carried out, therefore can not quicken the reaction of methyl esters and alkali;
2. in order to make soap body have suitable flowability, the concentration of soap is limited in 60-70% usually in the soap body;
3. soap body dry removal methyl alcohol and excessive water are subjected to very big restriction, and usually wayward;
4. the system that the Methanol Recovery circulation entered is quite complicated, relates to multistep processing.
Summary of the invention
Now find to adopt thorough mixing, and, can the fatty acid methyl ester of producing be carried out saponification and generate soap again by thorough mixing by fat and oily raw material production fatty acid methyl ester." thorough mixing " used herein is meant and adds in the stirred vessel that has condenser of sealing being usually used in producing the raw material of fatty acid methyl ester such as suitable triglyceride level, methyl alcohol and basic catalyst such as NaOH.Raw material in the container is rotated with common circular orbit, and the independent swivel arrangement in making raw material simultaneously and being installed in this container contacts, and this swivel arrangement is with direction rotation reverse with raw material mobile initial direction or in the same way.Carry out the useful equipment of this technology and state in the US of Myers patent 4772434, it is incorporated herein by reference.In preparation methyl esters process, the container shown in the Myers patent preferably is equipped with heating jacket.The temperature of reactant so on demand can raise.In addition, it is desirable to this container one siphoning installation is housed, generate like this after the methyl esters, easily deglycerizin.Find that now fatty acid methyl ester can generate apace usually in about 15-60 minute, and easily reclaim and excessive methyl alcohol and the glycerine of purifying.
Preferably, it is high about 10% that used quantity of methyl alcohol forms required stoichiometric quantity than ester, and excessive methyl alcohol stirs reactant as reaction solvent better.In addition, although need not, preferably ending in reaction adds acid with neutralization bases, and this is because some free fatty acidies that generate can generate soap with alkali reaction.Ester and glycerine separated after the existence of soap can disturbance reponse be finished.This acidifying also can prevent the formation of triglyceride level, because alkali reaction also has certain reversibility.Although along with the rising speed of response of triglyceride level molecular weight has certain reduction (may descend owing to the rising of the solubleness of methyl alcohol in triglyceride level with its molecular weight), this method can be used various triglyceride level.In the method, it can overcome by improving temperature of reaction or improving well-mixed speed.Another advantage of present method comprises the high density glycerine that can reclaim up to about 70%, and in the steam cracking process of prior art, the glycerol concentration of recovery is 8-10%.Can easily glycerine be reclaimed from mixing tank by siphon or centrifugation.In addition, we find in the method, produce water hardly, can change places after reaction is finished like this and separate and the purifying unreacted methanol.Adopting well-mixed another advantage is to adopt the triglyceride level of lower grade to obtain high-quality ester as raw material, this is because the what is called " colour solid " that exists in triglyceride level (colorbody) can enter in the glycerine in migration, thereby does not appear in the ester.
Equally, adopt thorough mixing also very fast by the reaction of fatty acid methyl ester production soap.Though the same alkali of ester (being NaOH) is unmixing relatively, adopt " thorough mixing " to make reactant have good contact, thereby make the reaction that generates soap very fast.Speed of response is along with the increase of container pressurization and well-mixed speed is increased.If saponification reaction is complete, can apply vacuum to remove methyl alcohol to container.If need, apply vacuum serially to remove some water that exist in the soap.As previously mentioned, thorough mixing can be reverse or be carried out in the same way.If be installed in independent swivel arrangement in the container to rotate in the opposite direction with raw material mobile side, adverse current then takes place mix.On the contrary, if this swivel arrangement then carries out following current and mixes with the direction rotation identical with the effusive initial direction of raw material.Being preferably adverse current mixes.
Brief description of drawings
Fig. 1 is the skeleton view of mixing equipment, and this equipment is suitable for providing sufficient mixing with from suitable fat and oily raw material production fatty acid methyl ester and these esters are carried out saponification produce soap.
Fig. 2 is the level view of the mixing equipment of Fig. 1.
Fig. 3 is the horizontal sectional drawing of the mixing equipment of Fig. 1 of being got along the line 3-3 of Fig. 1 basically.
Fig. 4 is the fragmentary cross-sectional view of the mixing equipment of Fig. 1-3 of being got along the line 4-4 of Fig. 3 basically.
Fig. 5-the 7th is used for the skeleton view of revolving fragment of the mixing equipment of Fig. 1-4.
The description of preferred embodiment
Term used herein " fat and oily raw material " is meant the raw material that custom adopts in soapmaking, and as natural fat and oil, it is the triglyceride level that three fatty group use glycerine (butter, lard, Oleum Cocois, palm-kernel wet goods) to carry out esterification randomly.Term " saponification " or " saponification reaction " are meant that with general alkaline matter such as NaOH, KOH, soda ash etc. fatty acid methyl ester being carried out neutralization reaction produces soap." thorough mixing " is to instigate reactant liquid stream to move rapidly in mixing vessel with annular trace (as counterclockwise), simultaneously, the liquid stream of rapid movement is contacted with mixing device, and the reactant of this mixing device and rapid movement is reverse or be rotated in the same way.
With reference to the accompanying drawings, Fig. 1 is a kind of scheme that is used for mixing equipment of the present invention, generally is designated as 10.Mixing tank 10 is described with mixing pan 11 (seeing Fig. 3-4), and it is rotatably installed in the sealable container 12.Sealing container 12 is installed in again on the fuselage 13.Fuselage 13 tilts, and mixing pan 11 and horizontal plane are tilted, thereby reacts at mixing pan internal reaction thing helping by gravity.Hinged charging bole 14 provides and has led to the inner inlet of mixing tank (more particularly mixing pan 11).When charging bole 14 is closed, can provide airtight sealing.In the mixing pan bottom, this equipment also provides a watertight and gastight Dump gate 15 (see figure 3)s.After saponification reaction is finished, from this Dump gate, discharge soap.
Mixing pan 11 is driven by the motor 16 with container 12 adjacent installations.The required horsepower of motor depends on the size of used mixing pan and the characteristic of the composition batch of material processed naturally.As previously mentioned, mixing pan is installed rotatably, in specific embodiment shown in Figure 3, it rotates in a clockwise direction.At the top of mixing tank 10 and be positioned on the eccentric position of mixing pan 11 rotor assembly 17 is installed.Rotor assembly 17 is provided with independent motor 18 (see figure 2)s of an adjustable-speed, thereby the speed of rotor assembly can be changed as required.With reference to Fig. 5, rotor assembly is formed by axle 19 with the annex 20 that rotor assembly is fixed on the CD-ROM drive motor.Various mixing tools can be installed on the axle 19, Fig. 5-7 is exactly some examples.
The mixing tool of Fig. 5 is formed by being generally circular plate 21, and its underpart is equipped with pin 22.Fig. 3 and 4 illustrates as disclosed rotor assembly among Fig. 5, and should be noted that this rotor assembly is installed in the mixing pan prejudicially, and with the reverse direction rotation of the sense of rotation of mixing pan.
The mixing tool of Fig. 6 is made up of two pairs of bars or cutter 24, and these two pairs of bars or cutter are installed with the angle of perpendicular mutually, if need to adorn a counterweight to keep balance.
Although the mixed graph of the mixing tool of Fig. 5 and 6 has certain difference, its mixing ability does not have marked difference.
Will be appreciated that rotor assembly with reverse or have three kinds of functions when mixing in the same way, promptly liquid mixing prepares soap; Chopping dough and the granulation of soap product.Can the fine rotor assembly of finishing these functions be shown in Fig. 7.The mixing tool of Fig. 7 is made up of plectane 21, and pin 29 is installed under it.Plate 21 tops are equipped with pin 30 and 31, sell 31 top, horizontal and are fixed with chopper blade 32.These blades 32 are installed in pin 31 tops with for when fluid mixture is semi-solid state or non-sticky, just be in contact with it.
With reference to Fig. 1 and 2, therefrom can see a condenser 36 is installed on the top of sealable container 12.Mixing pan 11 (seeing Fig. 3-4) communicates with condenser 36 by steam conduit 37.Although condenser 36 is inner not shown, it is constructed in a usual manner.Condenser 36 inside are the cooling tube of a series of cooling-water flowing warps.Water coolant is added by coolant port 38 from the top of water cooler, and discharges from the bottom of water cooler through the cryogen discharge (not shown).When contacting with cooling tube (cooling tube must be cooled under the dew point of hot water and steam and pure steam) from the water vapor of the heat of mixing pan or excessive alcohol, hot water and steam and/or alcohol are condensed into liquid on cooling tube, discharge from condenser 36 through water relief outlet 39 then.
In following mode, can on the mixing equipment of Fig. 1-4, apply vacuum.Vacuum port 40 on the condenser 36 communicates with the condenser internal chamber, and the condenser internal chamber communicates with mixing pan 11 by steam conduit 37 again conversely.The vacuum known devices of energy of counting arbitrarily can be linked to each other with vacuum port 40 to produce vacuum.Term used herein " vacuum " is meant in container 12 pressure inside that seal less than ambient atmosphere pressure.In the scheme of Fig. 1 and 2, use the vacuum pump of a conventional design.The size of vacuum pump depends on the size and the required vacuum tightness of used mixing equipment.
The device that is installed in the mixing pan 11 is can stand the thorough mixing operation in order to ensure the material in the mixing pan.These devices are fixed on just on the part of the mixing equipment on the mixing pan.As shown in Fig. 3 and 4, it is made up of the dish wall scraper 41 and the baffle plate 42 of trying to get to the heart of a matter, and baffle plate 42 is connected on the dish.
With reference to the equipment of figure 1-4, in preparation fatty acid ester process, fatty and oily raw material is by charging opening 14 or be installed in suitable valve (not shown) adding on the container 12.After fat and oil added, mixing pan 11 began rotation, added methyl alcohol and alkali by charging opening or valve afterwards.Rotor assembly 17 begins rotation, and reactant carries out thorough mixing.If adopt adverse current to mix, dish 11 and rotor assembly 17 are by rotation shown in Figure 3.The generally very similar vortex that rotatablely moves of the mixture that is produced is shown in the arrow 50 that is interrupted.Fat that the preparation fatty acid methyl ester is used or oily raw material can be conventional those materials that adopt in making water-soluble soap.Fatty or oily raw material is preferably the liquid from its fusing point to about 170 (76.7 ℃).Then, add methyl alcohol or alkali so that reaction is carried out.Can add methyl alcohol and alkali by several modes.Methyl alcohol is heated to about 140 °F (60 ℃), and mixes, add mixing tank then with alkali.In addition, methyl alcohol and alkali can add separately, add methyl alcohol earlier, add alkali again.Used quantity of methyl alcohol forms required stoichiometric quantity than ester and exceeds about 10%.In addition, the reaction finish after, can add number acid such as sulfuric acid with in and free alkali.If behind the deglycerizin, ester will be converted into soap, then usually need not to add acid.
Adopting thorough mixing to prepare soap by fatty acid methyl ester is a kind of very fast technology.Methyl alcohol is important to the initiation that increases reaction, and 50% or 30% alkali (NaOH) can play very good effect.The alkali of higher concentration has reduced the dry phase of technology, but lower concentration (30%) is convenient to the formation of saponification reaction process homogeneous.
In the following embodiments, all technologies are all carried out in RO2 type mixing tank, and its Eirich Machines company by German Hardheim makes.Mixing tank is equipped with one and surrounds sealable container, a vacuum unit of mixing pan and be similar to the condenser shown in Fig. 1-4.All embodiment all adopt adverse current to mix.
Embodiment 1
Make fatty acid methyl ester by following raw materials according and technology:
60: 40 plam oils: palm-kernel oil 2000g
NaOH particle 10g
Methyl alcohol 800g
Sulfuric acid 20g
Technology
-oil mixt is added mixing tank, and be preheated to 80 ℃.
-methyl alcohol is heated to 60 ℃, and adds alkali.
The mixture of-methyl alcohol/alkali adds the mixing tank of tep reel, and mixing tank and dish promptly are respectively 36rpm and 580rpm with low speed rotation.
About 3 minutes of-rotor middling speed (1140rpm) rotation.
-start well heater, and add 50ml methyl alcohol.
Afterreaction was finished in-Yue 1 hour.
-add acid solution, and reaction mixture is separated.Phenomenon
-reaction was finished after 1 hour, layering occurred.
-add the acid back between glycerine and methyl esters layer, to form the saponification layer of a white, but may not be necessary.
Productive rate: 1935g methyl esters
578g glycerine
The 2513g overall yield
Embodiment 2
By following raw material and prepared fatty acid methyl ester:
60: 40 plam oils: palm-kernel oil 2000g
NaOH particle 10g
Methyl alcohol 800g technology
-methyl alcohol and alkali grain are preheated to 63 ℃ and add reactor.
-oil mixt is added reactor, mixing pan rotates with 36rpm, and temperature is 59 ℃.
-rotor rotates with 1140rpm.
Collect sample in-per 5 minutes and observe layering.
After-30 minutes, reaction is finished.
-remix 30 minutes separates to observe.
-collecting product also separates.Phenomenon
-in the presence of alcohol excess and alkali, reaction is accelerated.
-clearly need not add acid.
-productive rate: methyl esters 1788g
Glycerine 383g
Overall yield 2171g-is because the decline of sampling productive rate.
Following material of embodiment 3 usefulness and technology are carried out saponification to Uniphat A60 and palm kernel fatty acid formicester: 60: 40 Uniphat A60s: palm kernel acid methyl esters 1200g30%NaOH 580g methyl alcohol 220g
2000g technology
-methyl esters is added mixing tank, and be preheated to 80 ℃, mixing pan rotates with 36rpm.
-in mixing pan, add NaOH.
-slowly add methyl alcohol at 71 ℃.
After-reaction the beginning, rotor is with the 1140rpm high speed rotating, and maximum temperature is 79 ℃.
The methyl alcohol that-collection is excessive.Phenomenon
-reaction can be carried out well, finishes reaction in 30 minutes.
-reflux exchanger is not 100% effective, needs the water that cool off rather than the water of room temperature.
-the vacuum that applies is too fast-mixing tank and condenser vacuumized.
-moisture and volatile matter (baking oven) 16.1% alkali, 0.15%AV 214 free-fats.
Embodiment 4
Adopt 50%NaOH to repeat embodiment 3:
60: 40 Uniphat A60s: palm kernel acid methyl esters 1200g
50％NaOH 348g
Methyl alcohol 220g
2000g technology
-methyl esters and methyl alcohol add in the mixing tank, are preheated to 63 ℃.
-adding NaOH, mixing pan begins with low speed (36rpm) rotation, room temperature.
After-reaction the beginning, rotor reaches 1140rpm, and top temperature is 77 ℃.
The first alcohol and water that-collection is excessive.Phenomenon:
-be reflected in 17 minutes and finish, faster than 30%NaOH.
-collect 150g methyl alcohol/H
2O.
-M ﹠amp; V (baking oven), 14.7%; Alkali, 0.06%.
-product is than more being fibrous for the first time.
Embodiment 5
Repeat embodiment 4 with excessive methanol:
60: 40 Uniphat A60s: palm kernel acid methyl esters 1200g
50％NaOH 348g
1548g technology
-in mixing tank, add methyl esters, and be preheated to 72 ℃.
-slowly add NaOH at 81 ℃.
-add 25g methyl alcohol with initiation reaction.
Behind-the several minutes, when maximum temperature was 90 ℃, rotor was with (1140rpm) rotation at a high speed.
Add 100g H after-1 hour
2O.
-need not be dry.Phenomenon
-add methyl alcohol reaction beginning, but can not complete reaction.
-mixing adds 100g H after 1 hour
2O, product change and react, need not be dry.
-M ﹠amp; V (baking oven), 9.4%; Alkali, 0.28%.
It is important that-excessive methyl alcohol and/or water are finished for reaction.
Embodiment 6
Do not adopt excessive methyl alcohol to repeat the technology of embodiment 3.
60: 40 Uniphat A60s: palm kernel acid methyl esters 1200g
NaOH(30％) 580g
1780g technology
-in mixing tank, add methyl esters, and be preheated to 80 ℃.
-at room temperature slowly add NaOH.
-rotor is with (1140rpm) rotation at a high speed, reactionless generation after about 10 minutes.
-add 150ml methyl alcohol with increment 25ml, to reaction beginning in about 30 minutes.
Methyl alcohol and H that-collection is excessive
2O.Phenomenon:
Add 150ml methyl alcohol afterreaction to mixing tank and begin quick generation, this is necessary for reaction.87 ℃ of maximum temperature of reaction, M ﹠amp; V (baking oven), 23.8%; Alkali, 0.04%.
Embodiment 7
Methyl esters 1200g
50％NaOH 348g
Methyl alcohol 200g
1748g technology
-mixing oil adds in the reactor, and is heated to 79 ℃.
Add methyl alcohol under the-room temperature.
-slowly adding NaOH, mixing pan begins slow rotation.
-be reflected in about 30 minutes and finish.
Claims (11)
1. by the fat commonly used in the soapmaking and the method for the water-soluble soap of oily raw material production, it comprises the steps: to generate fatty acid methyl ester by described fat and oil earlier: described fat and oil and methyl alcohol are joined in the airtight mixing vessel together with the alkali as catalyzer, make above-mentioned substance in described container through sufficient adverse current or mix one competent period fully in the same way so that described fat and oil are converted into fatty acid methyl ester, remove formed glycerine in the ester production process; Adding in described methyl esters afterwards is enough to make the alkali of described methyl esters saponified amount together with other methyl alcohol; With with described material through sufficient adverse current or mix in the same way, thereby make described methyl esters generation saponification reaction.
2. the process of claim 1 wherein that described material mixes through adverse current.
3. the method for claim 2, wherein said container are equipped with condenser and apply the device of vacuum or pressure.
4. the method for claim 3, wherein used adverse current swivel arrangement is installed in the described container prejudicially from the certain distance of described wall of container in adverse current is mixed.
5. the method for claim 4, wherein said fat and oily raw material are the liquid from its fusing point to 76.7 ℃.
6. the method for claim 5 wherein joins methyl alcohol in described fat and the oily raw material and is in excess in ester and forms required stoichiometric quantity.
7. the method for claim 6, wherein said excessive be 10%.
8. the method for claim 7, the concentration of used alkali is 30%-50% in the wherein said saponification reaction.
9. the method for claim 8 wherein apply vacuum removing the methyl alcohol that forms in the described saponification step, and described methyl alcohol condenses through described condenser.
10. method of producing fatty acid methyl ester by fat and oil, comprise: described fat and oil and methyl alcohol are joined in the airtight mixing vessel together with the alkali as catalyzer, make above-mentioned substance in described container through the sufficient adverse current of sufficiently long for some time or mix so that described fat and oil are converted into fatty acid methyl ester in the same way fully, afterwards glycerine is separated from described ester.
11. carrying out adverse current, the method for claim 10, wherein said material mix.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95197987 CN1087029C (en) | 1995-11-17 | 1995-11-17 | Production of fatty acid methyl esters and soap therefrom |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95197987 CN1087029C (en) | 1995-11-17 | 1995-11-17 | Production of fatty acid methyl esters and soap therefrom |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1244188A CN1244188A (en) | 2000-02-09 |
| CN1087029C true CN1087029C (en) | 2002-07-03 |
Family
ID=5083479
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 95197987 Expired - Fee Related CN1087029C (en) | 1995-11-17 | 1995-11-17 | Production of fatty acid methyl esters and soap therefrom |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1087029C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101328432B (en) * | 2008-04-23 | 2011-08-17 | 涂晶 | Apparatus for lubricating grease continuous saponification |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101195572B (en) * | 2006-12-08 | 2010-06-09 | 四川古杉油脂化学有限公司 | Method for synthesizing fatty acid methyl ester |
| GB2457023A (en) * | 2008-01-29 | 2009-08-05 | Quicksilver Ltd | Transesterification of vegetable oils |
| CN102391920A (en) * | 2011-09-30 | 2012-03-28 | 葛步春 | Method for preparing soap and soap powder by ester exchange method |
| CN108977291A (en) * | 2018-08-24 | 2018-12-11 | 韦艳才 | A kind of novel environment friendly soap lye and its production technology |
-
1995
- 1995-11-17 CN CN 95197987 patent/CN1087029C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101328432B (en) * | 2008-04-23 | 2011-08-17 | 涂晶 | Apparatus for lubricating grease continuous saponification |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1244188A (en) | 2000-02-09 |
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