CN105037145A - Process for preparing neopentyl polyol fatty acid ester by adopting prepared acid - Google Patents
Process for preparing neopentyl polyol fatty acid ester by adopting prepared acid Download PDFInfo
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- CN105037145A CN105037145A CN201510370608.8A CN201510370608A CN105037145A CN 105037145 A CN105037145 A CN 105037145A CN 201510370608 A CN201510370608 A CN 201510370608A CN 105037145 A CN105037145 A CN 105037145A
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- 239000002253 acid Substances 0.000 title claims abstract description 192
- 229920005862 polyol Polymers 0.000 title claims abstract description 105
- 235000014113 dietary fatty acids Nutrition 0.000 title claims abstract description 50
- 229930195729 fatty acid Natural products 0.000 title claims abstract description 50
- 239000000194 fatty acid Substances 0.000 title claims abstract description 50
- -1 neopentyl polyol fatty acid ester Chemical class 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 56
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- 238000011031 large-scale manufacturing process Methods 0.000 claims abstract description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 12
- 238000005886 esterification reaction Methods 0.000 claims abstract description 11
- 238000012360 testing method Methods 0.000 claims abstract description 9
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 93
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 92
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 69
- 150000003077 polyols Chemical class 0.000 claims description 67
- 239000000047 product Substances 0.000 claims description 50
- 229910052757 nitrogen Inorganic materials 0.000 claims description 46
- 239000000463 material Substances 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 39
- 239000007788 liquid Substances 0.000 claims description 39
- 238000001914 filtration Methods 0.000 claims description 38
- 230000015572 biosynthetic process Effects 0.000 claims description 35
- 238000003786 synthesis reaction Methods 0.000 claims description 35
- 238000000926 separation method Methods 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 235000021050 feed intake Nutrition 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 28
- 229940059574 pentaerithrityl Drugs 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 24
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 24
- 238000005070 sampling Methods 0.000 claims description 22
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 21
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 20
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 claims description 19
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 18
- 238000005516 engineering process Methods 0.000 claims description 17
- 239000006227 byproduct Substances 0.000 claims description 15
- 230000004044 response Effects 0.000 claims description 14
- 238000001179 sorption measurement Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 229960000892 attapulgite Drugs 0.000 claims description 12
- 238000009775 high-speed stirring Methods 0.000 claims description 12
- 229910052625 palygorskite Inorganic materials 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 11
- 150000004665 fatty acids Chemical class 0.000 claims description 11
- 239000000839 emulsion Substances 0.000 claims description 10
- 230000032050 esterification Effects 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- 238000013019 agitation Methods 0.000 claims description 7
- 238000005086 pumping Methods 0.000 claims description 7
- 238000007670 refining Methods 0.000 claims description 7
- 238000012952 Resampling Methods 0.000 claims description 2
- 238000004945 emulsification Methods 0.000 claims description 2
- 238000005259 measurement Methods 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 3
- 150000007513 acids Chemical class 0.000 abstract 3
- 150000002763 monocarboxylic acids Chemical class 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 15
- 150000002148 esters Chemical class 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- 239000008346 aqueous phase Substances 0.000 description 8
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 4
- 239000005639 Lauric acid Substances 0.000 description 4
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000002632 lipids Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 206010019233 Headaches Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/56—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation process of neopentyl polyol fatty acid ester, which is characterized in that for prepared acids prepared from different purchased batches of neopentyl polyol and monocarboxylic acids with different carbon atoms, the theoretical molar ratio required by complete esterification reaction with the prepared acids is determined according to the number of hydroxyl groups in the molecule of the neopentyl polyol or mixed neopentyl polyol, or a plurality of small test tests are carried out according to the empirical molar ratio formed by the neopentyl polyol or mixed neopentyl polyol and the prepared acids, when the small samples meet the conditions, the tests are ended, and the raw material batch and the raw material ratio of the last small test are used as the raw material ratio for large-scale production for production. The invention has the advantages that: the preparation process of the neopentyl polyol fatty acid ester can fully utilize the raw materials, reduce the trouble of post-treatment of the product and obtain the product with lower pour point.
Description
Technical field
The invention belongs to organic chemistry raw material and manufacture field, particularly the unary fatty acid of the different carbonatoms of a kind of use is mixed with the preparation technology of the amyl-based polyol fatty acid ester that preparating acid synthesized afterwards.
Background technology
In numerous fatty acid esters, a class fatty acid ester is had to have the special construction of quaternary carbon atom, also known as neopentyl structure, typical example as: pentaerythritol fatty ester, bis pentaervthritol ester, trimethylolpropane fatty acid ester, ditrimethylolpropane fatty acid ester, neopentyl glycol fatty acid ester, they enjoy the favor of people.Because the β position carbon atom of the carbonyl of these neo-pentyl fatty acid esters does not have hydrogen atom, so can not with the resonance structure of the carbon of the alcohol moiety of ester group and hydrogen evolution six atom cycloalkyl, only have high-energy could destroy such ester structure, this makes the stability of the oxidation-resistance of amyl-based polyol fatty acid ester and anti-elimination reaction fine.Thus amyl-based polyol fatty acid ester has the unrivaled superiority of other ester class, becomes the optimal selection of the high-end synthetic ester in current lubricating oil.
At these amyl-based polyol fatty acid esters, there are some esters because polyvalent alcohol used, as tetramethylolmethane, dipentaerythritol, ditrimethylolpropane, neopentyl glycol etc., their molecule symmetrically structure itself, so the ester that they and single lipid acid are synthesized also has symmetrical structure, and this kind of ester lattice at low temperatures with symmetrical structure is also very even, also just easy crystallization, thus just not there is mobility at a lower temperature, just limit the use of this kind of ester in the automobile oil of aviation engine lubricating oil, cold district.If but adopt mixing acid that the different unary fatty acid of several carbonatoms is mixed with as raw material, the structure of the ester be synthesized just has diversity, lattice when they are tending towards crystallization is at low temperatures also just not of uniform size, cause crystallization very difficult, thus needing at lower temperatures could crystallization.Like this, the amyl-based polyol fatty acid ester of this kind of preparating acid synthesis just has lower pour point, can use under extremely cold environment.
The technique document of current synthesis amyl-based polyol fatty acid ester series products is many, nothing more than employing direct esterification and ester-interchange method.Ester-interchange method owing to using basic catalyst, and can produce lower aliphatic alcohols etc. and has inflammable and byproduct that is explosion hazard, so in fact use seldom.Even employing direct esterification, be mostly adopt the excessive reaction forward of impelling of certain raw material to carry out, this will run into excessive raw material and the difficulty of product separation in follow-up purification, treating process.Even if adopt the means such as molecule rectifying to remove certain excessive raw material, even if can take off very thorough, also will inevitably cause the decline of target product yield, and the energy consumption that sepn process brings thus also can not be ignored, be thus difficult to synthesize the competitive product of price.
The current production technique display of some document reflection, in the process of synthesis amyl-based polyol fatty acid ester, adopts solvent or water entrainer to improve the efficiency of dehydration, makes esterification be unlikely to just can carry out at relatively high temperatures thoroughly.But one that adopts such technique to bring fearful effect finally will allow these solvents or water entrainer and product realize being separated thoroughly also very difficult.And the existence of a small amount of low boiling point solvent or water entrainer can cause the flash-point of product obviously to decline, at high temperature use to product and bring hidden danger.
The also current production technique display of some document reflection, in order to improve esterification yield, reduce the time of reaction, often adopts the excessive way of lipid acid to react, then carries out aftertreatment to product.To in the aftertreatment of product, mostly adopt neutralization, washing and point equal purification means.The consequence adopting such technology to bring is that the raw material of these acidity has loss, unit consumption is difficult to reach desirable level, production cost remains high.The salt produced in N-process is difficult to removing, and the process that will meet environmental requirement to the salt be in waste water is also a thing that make repeated headache.Because used alkaline matter in the process of aftertreatment, there is the situation of saponification reaction in the ester that also may occur to be synthesized, product is gone wrong again in follow-up use procedure.
Double the disclosed process data about synthetic ester, can find in current Technology in the selection of catalyzer, mostly the catalyzer of abandoning tradition, use load miscellaneous or composite catalyst instead.The cost in fact preparing various novel catalyzer is just higher, and the catalytic effect of these novel catalyzer is good not as good as traditional catalyst.Even if some solid catalyst can reclaim, but along with the effective constituent of in use solid-carried catalyst is constantly by wash-out, in fact these catalyzer can reusable restricted lifetime.
Because the source of raw material is different, production technique is also not quite similar, the index such as purity, foreign matter content of different batches raw material also exists trickle fluctuation, so qualified amyl-based polyol fatty acid ester will be produced, also need the feature for different batches raw material to carry out lab scale to grope, the proportioning of Reasonable adjustment raw material.
For the quality fluctuation of raw material between the deficiency of existing production amyl-based polyol fatty acid ester Product Process and different batches, in order to the lower amyl-based polyol fatty acid ester of pour point can be synthesized, be necessary to adopt the different unary fatty acid of several carbonatoms to get up by the mixed in molar ratio of setting and amyl-based polyol reacts, adopt the tosic acid be easy to get as catalyzer, in conjunction with determining rational proportioning between different batches raw material by lab scale, come economical, reasonably produce amyl-based polyol fatty acid ester.
Summary of the invention
After the unary fatty acid that the technical problem to be solved in the present invention is to provide the different carbonatoms of a kind of use is mixed with preparating acid and amyl-based polyol or mix new penta season polyvalent alcohol, employing tosic acid is catalyzer, economic and preparation technology that is reasonably amyl-based polyol fatty acid ester.
For solving the problems of the technologies described above, technical scheme of the present invention is: a kind of preparation technology of amyl-based polyol fatty acid ester, its innovative point is: the preparating acid be mixed with for the unary fatty acid that the amyl-based polyol purchasing the present lot come is different with several carbonatoms
First determine the theoretical molar proportioning of carrying out with such preparating acid completely needed for esterification according to amyl-based polyol used or the quantity that mixes hydroxyl in new penta season polyol molecule, or according to former for amyl-based polyol or mix new penta season polyvalent alcohol and the experience mol ratio that formed of such preparating acid select the mol ratio of current lab scale;
Adopt tosic acid as catalyzer, rely on heating to carry out esterification when logical nitrogen, and the water taken out of with nitrogen is collected by collection device, observe in collection device and no longer included after water deviates from 5 ~ 20 minutes, sampling, the acid number of working sample, makes current lab scale sample meet acid number≤1.5mgKOH/g by the adjustment of one or many lab scale mol ratio;
Add adsorption decolouriser, continue heated and stirred 0.5 ~ 2h, then heating is stopped, when being cooled to 50 ~ 70 DEG C in lab scale sample, suction filtration is carried out while hot in the Büchner funnel being covered with middling speed quantitative paper, product in filter flask is transferred in reagent bottle, the method specified according to GB/T7305-2003, measure the separation property of synthesis liquid and water; After if the result display high-speed stirring recorded terminates within three ten minutes left standstill after, the volume of emulsion layer is less than 3mL, then represent that the separation property of this synthesis liquid and water is good, terminate this lab scale;
Acid number≤1.5mgKOH/g in this lab scale and synthesis liquid and water separation property also satisfactory lab scale mol ratio carry out large-scale production as the proportioning raw materials of present lot raw material.
Further, described concrete steps are as follows:
step S1:the amyl-based polyol of present lot that buying is come and the unary fatty acid of different carbonatoms, first the mixed in molar ratio of unary fatty acids different for several carbonatoms by setting is got up, calculate this mixing acid amount to molecular weight, the quantity calculating amyl-based polyol used or mix hydroxyl in new penta season polyol molecule determines the theoretical molar proportioning of carrying out with such preparating acid completely needed for esterification, according to former for amyl-based polyol or mix new penta season polyvalent alcohol and such preparating acid formed experience mol ratio carry out lab scale test, if the quantity of amounting to hydroxyl of the hydroxyl value of amyl-based polyol used or mixing amyl-based polyol is n, then preparating acid and amyl-based polyol or mix amyl-based polyol theoretical molar than being n,
step S2:set amyl-based polyol in this lab scale or mix new penta season polyvalent alcohol and the mol ratio of preparating acid be 0.9:n ~ 1.3:n;
step S3:carry out lab scale, in the three-necked bottle of 500mL, first put into magnetic stir bar, drop into the preparating acid of 0.4 ~ 2.4mol, then according to the mol ratio that sets in step S2 drop into respective amount amyl-based polyol or mix new penta season polyvalent alcohol, open the intensification switch of oil bath heater, material in still is heated, when temperature in the kettle is raised to 110 ± 4 DEG C, add preparating acid and amyl-based polyol used or mix new penta season polyvalent alcohol always feed intake quality 0.5 ~ 2% tosic acid as catalyzer, under nitrogen tube is inserted into liquid level, nitrogen is passed into the flow velocity of 10 ~ 100mL/min, open the stirring of stirrer in magnetic agitation still, timing from now, material in still is warmed up to 120 ~ 250 DEG C, heating 5 ~ 24h, the water of observing response by-product is deviate to the speed conditions in collection device under the drive of nitrogen, by the time no longer included after a water deviates from collection device in 5 ~ 20 minutes, sampling,
step S4:the acid number of working sample, if the acid number≤1.5mgKOH/g of sample, then leaps to step S9; If the acid number > 1.5mgKOH/g of sample, then enter next step;
step S5:continue reaction 0.5 ~ 2h;
step S6:the reacted acid number of sampling and measuring, if acid number≤1.5mgKOH/g, then jumps to step S9; If acid number > is 1.5mgKOH/g, then enter next step;
step S7:judge the absolute value of acid number and the adjacent last hypo acid value difference measured in above-mentioned steps S6, if this absolute value > is 0.5mgKOH/g, then return step S5; If this absolute value≤0.5mgKOH/g, then enter next step;
step S8:if acid number is > 1.5mgKOH/g still, then terminate this lab scale, and return step S2 again adjust in the scope of 0.9:n ~ 1.3:n and set once amyl-based polyol or mix new penta season polyvalent alcohol and the concrete mol ratio tested of preparating acid lab scale; If acid number≤1.5mgKOH/g, then enter next step;
step S9:in three-necked bottle, add amyl-based polyol used or mix new penta season polyvalent alcohol and preparating acid always feed intake quality 0.5 ~ 5%, particle diameter is the adsorption decolouriser of 65 ~ 80 μm, continue heated and stirred 0.5 ~ 2h, then heating is stopped, when being cooled to 50 ~ 70 DEG C in lab scale sample, in the Büchner funnel being covered with middling speed quantitative paper, carry out suction filtration while hot, the product in filter flask is transferred in reagent bottle;
step S10:according to the method that GB/T7305-2003 specify, synthesis liquid in mensuration reagent bottle and the separation property of water, if be less than 3mL at the volume of the three ten minutes internal emulsification layers left standstill after the result display high-speed stirring recorded terminates, then represent that the separation property of this synthesis liquid and water is good, terminate this lab scale, write down this batch of preparating acid used and the suitable mol ratio of amyl-based polyol, using the mol ratio of this lab scale as proportioning raw materials when carrying out large-scale production with the raw material of present lot; If the separation property of measurement result display synthesis liquid and water is bad, then return step S2
,in the test of fine setting lab scale preparating acid and amyl-based polyol or mix new penta season polyvalent alcohol concrete mol ratio, then carry out lab scale next time;
step S11:large-scale production;
Further, the step of described large-scale production is specially:
step S111:the present lot obtained with lab scale amyl-based polyol used or mix new penta season polyvalent alcohol and the mol ratio of preparating acid, at 2M
3reactor in, drop into preparating acid and amyl-based polyol or mix new penta season polyvalent alcohol, the total mass of raw material in still is made to be in the scope of 500 ~ 1500kg, open and stir, during beginning, rotating speed maintains 5 ~ 50rpm, open the heating valve of reactor, material in still is heated, when temperature in the kettle is raised to 115 ± 5 DEG C, add preparating acid and amyl-based polyol used or mix new penta season polyvalent alcohol always feed intake quality 0.5 ~ 2% tosic acid as catalyzer, open nitrogen valve, nitrogen is passed into the flow velocity of 1 ~ 100L/min, the rotating speed of stirring is brought up to 50 ~ 300rpm, timing from now, material in still is warmed up to 120 ~ 250 DEG C, heating 5 ~ 24h, the water of observing response by-product is deviate to the speed conditions in collection device under the drive of nitrogen, by the time no longer included after a water deviates from collection device in 5 ~ 20 minutes, sampling, the acid number of working sample,
step S112:if the acid number of sample can not reach≤level of 1.5mgKOH/g, then carry out reaction 0.5 ~ 2h, resampling detects acid number, until the acid number≤1.5mgKOH/g of sample;
step S113:in reactor, add amyl-based polyol used or mix new penta season polyvalent alcohol and preparating acid always feed intake quality 0.1 ~ 2% adsorption decolouriser, continue heated and stirred 0.5 ~ 3h, then heating is stopped, when being cooled to 50 ~ 70 DEG C Deng the temperature of product in still, open the valve at the bottom of still, with refining filtering pump by flow out material pumping in pressure filter, order number is adopted to be 250 ~ 300 object filter screens, carry out circulation press filtration, press filtration material out turns back in reactor, the color that circulation press filtration proceeds to the product returned do not seen adsorption decolouriser particle residual till, product after press filtration being decoloured pours in pail pack.
Further, described amyl-based polyol or mix new penta season polyvalent alcohol be one or more in ditrimethylolpropane, tetramethylolmethane, dipentaerythritol, neopentyl glycol.
Further, described adsorption decolouriser can be gac, atlapulgite, attapulgite, diatomite.
Further, when described adsorption decolouriser is gac, can use together in conjunction with diatomite, attapulgite, atlapulgite.
The invention has the advantages that:
(1) each batch of raw material owing to buying has trickle fluctuation in purity, so adopt in the theoretical molar proportioning of corresponding raw material or the basis of experience mol ratio, the raw material of each batch is first adjusted to their proportioning by lab scale, until the acid number of amyl-based polyol fatty acid ester that lab scale is synthesized both met the requirements, also after meeting the requirements with the separation property of water, the feed molar proportioning adopting this suitable again goes to carry out large-scale production, raw material can be made to be fully utilized, ensure the quality of product, eliminate the highly energy-consuming that molecule rectifying is such, the lossy post-processing step of product, make production process economy, rationally, product has the market competitiveness.
(2) need not as current some processes, high, the not poisonous organic solvent of the boiling point such as toluene, dimethylbenzene is adopted to go as water entrainer, avoid the Dangerous and Harmful Factors in operating process, there is not the residual of low-boiling-point substance in product, thus ensure that the amyl-based polyol fatty acid ester be synthesized can at high temperature use.
(3) lipid acid owing to not adopting some traditional technologys to adopt is excessive, and then the technique that neutralizes is carried out with alkaline solution, eliminate washing and point equal post-processing step, and reluctant salts substances can not be produced, make that production process seems succinctly, environmental protection, avoid the product that is synthesized in the basic conditions again by the risk of saponification, hydrolysis.
(4) adopt traditional tosic acid as catalyzer, conveniently be easy to get, not exist batch between the discrepant problem of catalytic activity, it also has a benefit, be exactly that its fusing point is about 106 DEG C, after reaction end product cools down, in the process of decolorization filtering, the tosic acid of separating out from system can be filtered out together, realize being separated of catalyzer and product.
(5) when adopting gac as adsorption decolouriser, when gac price is higher, be combined the porousness sorbent material that diatomite, attapulgite, atlapulgite etc. are inexpensive, can the rational thickness of filter bed of heap, both be enough to play good filtration decolorizing effect in suction filtration or circulation pressure-filtering process, and effectively can have reduced again the cost of decolorization.
(6) adopt mixing acid that the different unary fatty acid of several carbonatoms is mixed with as raw material, the structure of the ester be synthesized has diversity, lattice when they are tending towards crystallization is at low temperatures also just not of uniform size, causes crystallization very difficult, thus will at lower temperatures could crystallization.The amyl-based polyol fatty acid ester of this kind of preparating acid synthesis just has very low pour point, can use under extremely cold environment.
Embodiment
The following examples can make the present invention of professional and technical personnel's comprehend, but therefore do not limit the present invention among described scope of embodiments.
embodiment 1
A preparation method for amyl-based polyol fatty acid ester, adopt tetramethylolmethane and preparating acid to be raw material, concrete steps are as follows:
step S1:for buying come present lot tetramethylolmethane, C5 acid, C7 is sour and C9 is sour, first C5 acid, the sour and sour molar percentage by 15:70:15 of C9 of C7 are mixed, calculate the molecular weight of amounting to of this preparating acid is 130.18,4 hydroxyls are had in a tetramethylolmethane molecule, have 4 hydroxyls in a tetramethylolmethane molecule, then such preparating acid is 4 with the theoretical molar ratio of tetramethylolmethane;
step S2:set the mol ratio of preparating acid and tetramethylolmethane in this lab scale, synthesize according to front the experience drawn several times, the mol ratio that the preparating acid of tetramethylolmethane and such mol ratio is proper is 1.02:4;
step S3:carry out lab scale, in the three-necked bottle of 500mL, first put into magnetic stir bar, drop into 1.6mol(208.288g) preparating acid, then correspondingly drop into 0.408mol(55.549g) tetramethylolmethane, open the intensification switch of oil bath heater, material in still is heated, when temperature in the kettle is raised to 110 DEG C, add preparating acid and tetramethylolmethane always to feed intake the 1%(2.64g of quality 263.837g) tosic acid as catalyzer, under nitrogen tube is inserted into liquid level, nitrogen is passed into the flow velocity of 30mL/min, open the stirring of stirrer in magnetic agitation still, timing from now, material in still is warmed up to 180 ± 5 DEG C, heating 12h, the water of observing response by-product is deviate to the speed conditions in collection device under the drive of nitrogen, by the time no longer included after a water deviates from collection device in 10 minutes, sampling,
step S4:the acid number of working sample is 0.43mgKOH/g, because the acid number of sample reaches≤the level of 1.5mgKOH/g, subsequently jumps to step S9;
step S9:in three-necked bottle, adding tetramethylolmethane and preparating acid always to feed intake the 2%(5.28g of quality) particle diameter is the atlapulgite of 75 μm, continue heated and stirred 1h, then heating is stopped, when being cooled to 60 DEG C in lab scale sample, in the Büchner funnel being covered with middling speed quantitative paper, carry out suction filtration while hot, the product in filter flask is transferred in reagent bottle;
step S10:according to the method that GB/T7305-2003 specify, measure the separation property of synthesis liquid and water, the result recorded is when leaving standstill 20 minutes after high-speed stirring terminates, the volume of the emulsion layer between oil phase and aqueous phase is 2mL, represent that the separation property of this synthesis liquid and water is good, so need not adjust the mol ratio of this batch of tetramethylolmethane relative to preparating acid again; Terminate this lab scale, write down this batch of tetramethylolmethane used and the suitable mol ratio 1.02:4 of preparating acid;
step S11:large-scale production;
Be specially:
Step S111: the suitable mol ratio 1.02:4 adopting the tetramethylolmethane for present lot and the preparating acid obtained in above-mentioned steps, at 2M
3reactor in, drop into 781.08kg preparating acid and 208.31kg tetramethylolmethane, the total mass of raw material in still is made to reach 989.39kg, open and stir, during beginning, rotating speed maintains 15rpm, open the heating valve of reactor, material in still is heated, when temperature in the kettle is raised to 115 DEG C, add preparating acid and tetramethylolmethane always to feed intake the 1%(9.89kg of quality) tosic acid as catalyzer, open nitrogen valve, nitrogen is passed into the flow velocity of 15L/min, the rotating speed of stirring is brought up to 150rpm, timing from now, material in still is warmed up to 180 ± 5 DEG C, heating 12.5h, the water of observing response by-product is deviate to the speed conditions in collection device under the drive of nitrogen, by the time no longer included after a water deviates from collection device in 10 minutes, sampling, the acid number of working sample, for 0.48mgKOH/g,
Step S112: because the acid number of sample reaches≤the level of 1.5mgKOH/g, so need not proceed reaction again;
Step S113: add tetramethylolmethane and preparating acid and always feed intake the 0.6%(5.94kg of quality in reactor) particle diameter is the atlapulgite of 75 μm, continue heated and stirred 2h, then heating is stopped, when being cooled to 60 DEG C Deng the temperature of product in still, open the valve at the bottom of still, with refining filtering pump by flow out material pumping in pressure filter, order number is adopted to be 270 object filter screens, carry out circulation press filtration, press filtration material out turns back in reactor, after circulation press filtration carries out nine minutes, the color of the product returned has not seen the residual of atlapulgite particle, product after press filtration being decoloured pours in pail pack.
embodiment 2
A preparation method for amyl-based polyol fatty acid ester, adopt ditrimethylolpropane and preparating acid to be raw material, concrete steps comprise:
step S1:for buying come present lot ditrimethylolpropane, C5 acid, C6 is sour, C7 is sour and C8 is sour, first by C5 acid, C6 is sour, C7 is sour and the sour molar percentage by 25:25:25:25 of C8 mixes, calculate the molecular weight of amounting to of this preparating acid is 123.17, have 4 hydroxyls in a ditrimethylolpropane molecule, then preparating acid is 4 with the theoretical molar ratio of ditrimethylolpropane;
step S2:set the mol ratio of preparating acid and ditrimethylolpropane in this lab scale, the theoretical molar proportioning 1:4 of both employings carries out lab scale test;
step S3:carry out lab scale, in the three-necked bottle of 500mL, first put into magnetic stir bar, drop into 1.2mol(147.804g) preparating acid, then correspondingly drop into 0.312mol(78.103g) ditrimethylolpropane, open the intensification switch of oil bath heater, material in still is heated, when temperature in the kettle is raised to 110 DEG C, add preparating acid and ditrimethylolpropane always to feed intake the 1%(2.26g of quality 225.907g) tosic acid as catalyzer, under nitrogen tube is inserted into liquid level, nitrogen is passed into the flow velocity of 30mL/min, open the stirring of stirrer in magnetic agitation still, timing from now, material in still is warmed up to 160 ± 5 DEG C, heating 8.5h, the water of observing response by-product is deviate to the speed conditions in collection device under the drive of nitrogen, by the time no longer included after a water deviates from collection device in 10 minutes, sampling,
step S4:the acid number of working sample is 0.3mgKOH/g, because the acid number of sample reaches≤the level of 1.5mgKOH/g, subsequently leaps to conventional steps S9;
step S9:in three-necked bottle, adding ditrimethylolpropane and preparating acid always to feed intake the 0.6%(1.36g of quality) particle diameter is the gac of 75 μm, continue heated and stirred 1h, then heating is stopped, when being cooled to 60 DEG C in lab scale sample, be carry out suction filtration in the Büchner funnel of the diatomite of 75 μm and middling speed quantitative paper being covered with particle diameter while hot, the product in filter flask is transferred in reagent bottle;
step S10:according to the method that GB/T7305-2003 specify, measure the separation property of synthesis liquid and water, the result recorded is that when leaving standstill 30 minutes after high-speed stirring terminates, between oil phase and aqueous phase, the volume of emulsion layer is 4mL, represents that the separation property of this synthesis liquid and water is bad, the separation property of synthesizing liquid and water due to the result display recorded is bad, so for this batch of ditrimethylolpropane buied and with C5 acid, C6 acid, the preparating acid that C7 acid and C8 acid are made into, its mol ratio is adjusted to 1.03:4, drop into 1.2mol(147.804g) preparating acid, then correspondingly drop into 0.309mol(77.352g) ditrimethylolpropane, the rapid S3 of all the other course synchronization of lab scale synthesis, to the product sampling synthesized, recording its acid number is 0.5mgKOH/g, proceed decolouring, filter, then the separation property of synthesis liquid and water is measured, the result recorded is that high-speed stirring terminates rear leaving standstill after 15 minutes, between oil phase and aqueous phase, the volume of emulsion layer is 2mL, represent that the separation property of this synthesis liquid and water can accept, write down the raw material for this batch buied, suitable ditrimethylolpropane and the mol ratio of preparating acid are 1.03:4, using the proportioning raw materials of this lab scale as proportioning raw materials when carrying out large-scale production with the raw material of present lot,
step S11:large-scale production;
Be specially:
Step S111: the suitable mol ratio 1.03:4 adopting the ditrimethylolpropane for present lot and the preparating acid obtained in above-mentioned steps, at 2M
3reactor in, drop into 739.02kg preparating acid and 386.76kg ditrimethylolpropane, the total mass of raw material in still is made to reach 1125.78kg, open and stir, during beginning, rotating speed maintains 15rpm, open the heating valve of reactor, material in still is heated, when temperature in the kettle is raised to 115 DEG C, add preparating acid and ditrimethylolpropane always to feed intake the 0.8%(9.01kg of quality) tosic acid as catalyzer, open nitrogen valve, nitrogen is passed into the flow velocity of 20L/min, the rotating speed of stirring is brought up to 150rpm, timing from now, material in still is warmed up to 160 ± 5 DEG C, heating 9h, the water of observing response by-product is deviate to the speed conditions in collection device under the drive of nitrogen, by the time no longer included after a water deviates from collection device in 10 minutes, sampling, the acid number of working sample, for 0.52mgKOH/g,
Step S112: because the acid number of sample reaches≤the level of 1.5mgKOH/g, so need not proceed reaction again;
Step S113: add ditrimethylolpropane and preparating acid and always feed intake the 0.3%(3.38kg of quality in reactor) particle diameter is the gac of 75 μm, 0.15%(1.69kg) particle diameter is the diatomite of 75 μm, continue heated and stirred 1.5h, then heating is stopped, when being cooled to 60 DEG C Deng the temperature of product in still, open the valve at the bottom of still, with refining filtering pump by flow out material pumping in pressure filter, order number is adopted to be 270 object filter screens, carry out circulation press filtration, press filtration material out turns back in reactor, after circulation press filtration carries out eight minutes, the color of the product returned has not seen that the activated carbon granule of diatomite particle and black remains, product after press filtration being decoloured pours in pail pack.
embodiment 3
A preparation method for amyl-based polyol fatty acid ester, the preparating acid adopting dipentaerythritol and 2 ethyl hexanoic acid and lauric acid to be made into is raw material, and concrete steps are as follows:
step S1:2 ethyl hexanoic acid and lauric acid are mixed by the molar percentage of 50:50, calculate the molecular weight of amounting to of this mixing acid is 172.27,6 hydroxyls are had in a dipentaerythritol molecule, for the dipentaerythritol come with buying and this preparating acid be made into the preparating acid that 2 ethyl hexanoic acid and lauric acid are made into, its theoretical molar proportioning is 1:6;
step S2:set the mol ratio of preparating acid and amyl-based polyol in this lab scale, this lab scale first adopts the theoretical molar proportioning 1:6 of dipentaerythritol and such preparating acid;
step S3:carry out lab scale, in the three-necked bottle of 500mL, first put into magnetic stir bar, drop into 1.2mol(206.724g) preparating acid, then correspondingly drop into 0.2mol(50.856g) dipentaerythritol, open the intensification switch of oil bath heater, material in still is heated, when temperature in the kettle is raised to 110 DEG C, add preparating acid and dipentaerythritol always to feed intake the 1%(2.58g of quality 257.58g) tosic acid as catalyzer, under nitrogen tube is inserted into liquid level, nitrogen is passed into the flow velocity of 30mL/min, open the stirring of stirrer in magnetic agitation still, timing from now, material in still is warmed up to 245 ± 5 DEG C, heating 17h, the water of observing response by-product is deviate to the speed conditions in collection device under the drive of nitrogen, by the time no longer included after a water deviates from collection device in 10 minutes, sampling,
step S4:the acid number of working sample is 0.15mgKOH/g, because the acid number of sample reaches≤the level of 1.5mgKOH/g, leaps to the S9 of conventional steps so subsequent;
step S9:in three-necked bottle, adding dipentaerythritol and preparating acid always to feed intake the 0.6%(1.55g of quality) particle diameter is the gac of 75 μm, continue heated and stirred 1h, then heating is stopped, when being cooled to 60 DEG C in lab scale sample, be carry out suction filtration in the Büchner funnel of the attapulgite of 75 μm and middling speed quantitative paper being covered with particle diameter while hot, the product in filter flask is transferred in reagent bottle;
step S10:according to the method that GB/T7305-2003 specify, measure the separation property of synthesis liquid and water, the result recorded is that high-speed stirring terminates rear leaving standstill after 30 minutes, and between oil phase and aqueous phase, the volume of emulsion layer is 6mL, represents that the separation property of this synthesis liquid and water is bad;
The separation property of synthesizing liquid and water due to the result display recorded is bad, so for this batch of dipentaerythritol of buying and the preparating acid be made into by 2 ethyl hexanoic acid and lauric acid, its mol ratio is adjusted to 0.94:6, drop into 1.2mol(206.724g) preparating acid, then correspondingly drop into 0.188mol(47.805g) dipentaerythritol, the rapid S3 of all the other course synchronization of lab scale synthesis, to the product sampling synthesized, recording its acid number is 0.6mgKOH/g, proceed decolouring, filter, then the separation property of synthesis liquid and water is measured, the result recorded is that high-speed stirring terminates rear leaving standstill after ten minutes, between oil phase and aqueous phase, the volume of emulsion layer is 2mL, represent that the separation property of this synthesis liquid and water can accept, write down the raw material for this batch buied, suitable dipentaerythritol and the mol ratio of preparating acid are 0.94:6, using the proportioning raw materials of this lab scale as proportioning raw materials when carrying out large-scale production with the raw material of present lot,
step S11:large-scale production;
Be specially:
Step S111: the suitable mol ratio 0.94:6 adopting the dipentaerythritol for present lot and the preparating acid obtained in above-mentioned steps, at 2M
3reactor in, drop into the dipentaerythritol of 1033.62kg preparating acid and 239.023kg preparation, the total mass of raw material in still is made to reach 1272.643kg, open and stir, during beginning, rotating speed maintains 15rpm, open the heating valve of reactor, material in still is heated, when temperature in the kettle is raised to 115 DEG C, add preparating acid and mixing amyl-based polyol always to feed intake the 1%(12.73kg of quality) tosic acid as catalyzer, open nitrogen valve, nitrogen is passed into the flow velocity of 20L/min, the rotating speed of stirring is brought up to 100rpm, timing from now, material in still is warmed up to 245 ± 5 DEG C, heating 18h, the water of observing response by-product is deviate to the speed conditions in collection device under the drive of nitrogen, by the time no longer included after a water deviates from collection device in 10 minutes, sampling, the acid number of working sample, for 0.64mgKOH/g,
Step S112: because the acid number of sample reaches≤the level of 1.5mgKOH/g, so need not proceed reaction again;
Step S113: add the mixing amyl-based polyol of preparation and preparating acid and always feed intake the 0.4%(5.09kg of quality in reactor) gac, 0.2%(2.55kg) particle diameter is the attapulgite of 75 μm, continue heated and stirred 1.5h, then heating is stopped, when being cooled to 60 DEG C Deng the temperature of product in still, open the valve at the bottom of still, with refining filtering pump by flow out material pumping in pressure filter, employing order number is that the filter screen of 270 μm carries out circulation press filtration, press filtration material out turns back in reactor, after circulation press filtration carries out 12 minutes, the color of the product returned has not seen the residual of the gac of black and the attapulgite particle of brown, product after press filtration being decoloured pours in pail pack.
embodiment 4
A preparation method for amyl-based polyol fatty acid ester, the mixing amyl-based polyol that employing mass percent accounts for the tetramethylolmethane of 90%, the dipentaerythritol of 10% forms and preparating acid are raw material, and concrete steps are as follows:
step S1:4 hydroxyls are had in a tetramethylolmethane molecule, 6 hydroxyls are had in a dipentaerythritol molecule, account for the tetramethylolmethane of 90% by mass percent, the molecular-weight average of mixing amyl-based polyol that the dipentaerythritol of 10% forms is 142.783, amounting to hydroxyl value is 4.112; The C5 buied acid, the sour and sour molar percentage by 40:40:20 of C9 of C7 are mixed, calculate the molecular weight of amounting to of this mixing acid is 124.57, for this mixing amyl-based polyol be mixed with by tetramethylolmethane and dipentaerythritol, be 1:4.112 relative to the theoretical molar proportioning of the preparating acid become by such molar ratio;
step S2:set the mol ratio of preparating acid and amyl-based polyol in this lab scale, this lab scale first adopts the theoretical molar proportioning 1:4.112 of this mixing amyl-based polyol and such preparating acid;
step S3:carry out lab scale, in the three-necked bottle of 500mL, first put into magnetic stir bar, drop into 1.234mol(153.681g) preparating acid, then correspondingly drop into 0.3mol(42.835g) mixing amyl-based polyol, open the intensification switch of oil bath heater, material in still is heated, when temperature in the kettle is raised to 110 DEG C, add preparating acid and dipentaerythritol always to feed intake the 1%(1.97g of quality 196.516g) tosic acid as catalyzer, under nitrogen tube is inserted into liquid level, nitrogen is passed into the flow velocity of 30mL/min, open the stirring of stirrer in magnetic agitation still, timing from now, material in still is warmed up to 240 ± 5 DEG C, heating 18h, the water of observing response by-product is deviate to the speed conditions in collection device under the drive of nitrogen, by the time no longer included after a water deviates from collection device in 10 minutes, sampling,
step S4:the acid number of working sample is 0.21mgKOH/g, because the acid number of sample reaches≤the level of 1.5mgKOH/g, leaps to the S9 of conventional steps so subsequent;
step S9:in three-necked bottle, adding mixing amyl-based polyol and preparating acid always to feed intake the 1%(1.97g of quality) particle diameter is the attapulgite of 75 μm, continue heated and stirred 1h, then heating is stopped, when being cooled to 60 DEG C in lab scale sample, in the Büchner funnel being covered with middling speed quantitative paper, carry out suction filtration while hot, the product in filter flask is transferred in reagent bottle;
step S10:according to the method that GB/T7305-2003 specify, measure the separation property of synthesis liquid and water, the result recorded is that high-speed stirring terminates rear leaving standstill after 30 minutes, and between oil phase and aqueous phase, the volume of emulsion layer is 5mL, represents that the separation property of this synthesis liquid and water is bad;
The separation property of synthesizing liquid and water due to the result display recorded is bad, so for mixing neo-pentyl how far alcohol and the preparating acid of this batch, its mol ratio is adjusted to 0.98:4.112, drop into 1.234mol(153.681g) preparating acid, then correspondingly drop into 0.294mol(41.978g) mixing amyl-based polyol, the rapid S3 of all the other course synchronization of lab scale synthesis, to the product sampling synthesized, recording its acid number is 0.42mgKOH/g, proceed decolouring, filter, then the separation property of synthesis liquid and water is measured, the result recorded is that high-speed stirring terminates rear leaving standstill after 25 minutes, between oil phase and aqueous phase, the volume of emulsion layer is 2mL, represent that the separation property of this synthesis liquid and water can accept, write down the raw material for this batch buied, suitable mixing amyl-based polyol and the mol ratio of preparating acid are 0.98:4.112, using the proportioning raw materials of this lab scale as proportioning raw materials when carrying out large-scale production with the raw material of present lot,
step S11:large-scale production;
Be specially:
Step S111: adopt in above-mentioned steps obtain for the mixing amyl-based polyol of present lot and the suitable mol ratio 0.98:4.112 of preparating acid, at 2M
3reactor in, drop into the mixing amyl-based polyol of 996.56kg preparating acid and 272.213kg preparation, the total mass of raw material in still is made to reach 1268.773kg, open and stir, during beginning, rotating speed maintains 15rpm, open the heating valve of reactor, material in still is heated, when temperature in the kettle is raised to 115 DEG C, add preparating acid and mixing amyl-based polyol always to feed intake the 1%(12.69kg of quality) tosic acid as catalyzer, open nitrogen valve, nitrogen is passed into the flow velocity of 20L/min, the rotating speed of stirring is brought up to 100rpm, timing from now, material in still is warmed up to 240 ± 5 DEG C, heating 19h, the water of observing response by-product is deviate to the speed conditions in collection device under the drive of nitrogen, by the time no longer included after a water deviates from collection device in 10 minutes, sampling, the acid number of working sample, for 0.45mgKOH/g,
Step S112: because the acid number of sample reaches≤the level of 1.5mgKOH/g, so need not proceed reaction again;
Step S113: add the mixing amyl-based polyol of preparation and preparating acid and always feed intake the 0.6%(7.61kg of quality in reactor) attapulgite, continue heated and stirred 2h, then heating is stopped, when being cooled to 60 DEG C Deng the temperature of product in still, open the valve at the bottom of still, with refining filtering pump by flow out material pumping in pressure filter, employing order number is that the filter screen of 270 μm carries out circulation press filtration, press filtration material out turns back in reactor, after circulation press filtration carries out 11 minutes, the color of the product returned has not seen the residual of the attapulgite particle of brown, product after press filtration being decoloured pours in pail pack.
embodiment 5
A preparation method for amyl-based polyol fatty acid ester, adopt neopentyl glycol and preparating acid to be raw material, concrete steps are as follows:
step S1:by the C5 buied acid, C6 is sour, C7 is sour, C8 is sour and the sour molar percentage by 10:20:40:20:10 of C9 mixes, calculate the molecular weight of amounting to of this mixing acid is 130.18, have 2 hydroxyls in a neopentyl glycol molecule, then preparating acid and the theoretical molar of neopentyl glycol are than being 2:1;
step S2:set the mol ratio of preparating acid and neopentyl glycol in this lab scale, synthesize according to front the experience drawn several times, neopentyl glycol and the proper mol ratio of such preparating acid are 1:2;
step S3:in the three-necked bottle of 500mL, first put into magnetic stir bar, drop into 1.6mol(208.288g) preparating acid, then correspondingly drop into 0.8mol(83.32g) neopentyl glycol, open the intensification switch of oil bath heater, material in still is heated, when temperature in the kettle is raised to 110 DEG C, add preparating acid and neopentyl glycol always to feed intake the 1%(2.916g of quality 291.608g) tosic acid as catalyzer, under nitrogen tube is inserted into liquid level, nitrogen is passed into the flow velocity of 30mL/min, open the stirring of stirrer in magnetic agitation still, timing from now, material in still is warmed up to 140 ± 5 DEG C, heating 7h, the water of observing response by-product is deviate to the speed conditions in collection device under the drive of nitrogen, by the time no longer included after a water deviates from collection device in 10 minutes, sampling,
step S4:the acid number of working sample is 1.7mgKOH/g, because the acid number of sample does not reach≤the level of 1.5mgKOH/g, therefore enters next step;
step S5:continue reaction 1h;
step S6:sampling, the acid number of working sample is 1.3mgKOH/g; Because its acid number reaches≤the level of 1.5mgKOH/g, the therefore subsequent S9 leaping to conventional steps;
step S9:in three-necked bottle, add neopentyl glycol and preparating acid always to feed intake the 2%(5.832g of quality) particle diameter be the diatomite of 75 μm, continue heated and stirred 1h, then heating is stopped, when being cooled to 60 DEG C in lab scale sample, in the Büchner funnel being covered with middling speed quantitative paper, carry out suction filtration while hot, the product in filter flask is transferred in reagent bottle;
step S10:according to the method that GB/T7305-2003 specify, measure the separation property of synthesis liquid and water, the result recorded be high-speed stirring terminate rear leave standstill five minutes time, between oil phase and aqueous phase, the volume of emulsion layer is 1mL, represent that the separation property of this synthesis liquid and water is good, writing down this batch of neopentyl glycol and the suitable mol ratio of preparating acid, is 1:2, using the proportioning raw materials of this lab scale as proportioning raw materials when carrying out large-scale production with the raw material of present lot; The separation property of synthesizing liquid and water due to the result display recorded is good, so need not adjust the mol ratio of this batch of neopentyl glycol relative to preparating acid again;
step S11:large-scale production;
Be specially:
Step S111: the suitable mol ratio 1:2 adopting the neopentyl glycol for present lot and the preparating acid obtained in above-mentioned steps, at 2M
3reactor in, drop into 781.08kg preparating acid and 312.45kg neopentyl glycol, the total mass of raw material in still is made to reach 1093.53kg, open and stir, during beginning, rotating speed maintains 15rpm, open the heating valve of reactor, material in still is heated, when temperature in the kettle is raised to 115 DEG C, add preparating acid and neopentyl glycol always to feed intake the 1%(10.935kg of quality) tosic acid as catalyzer, open nitrogen valve, nitrogen is passed into the flow velocity of 20L/min, the rotating speed of stirring is brought up to 160rpm, timing from now, material in still is warmed up to 140 ± 5 DEG C, heating 8.5h, the water of observing response by-product is deviate to the speed conditions in collection device under the drive of nitrogen, by the time no longer included after a water deviates from collection device in 10 minutes, sampling, the acid number of working sample, for 1.35mgKOH/g,
Step S112: because the acid number of sample reaches≤the level of 1.5mgKOH/g, so need not proceed reaction again;
Step S113: add neopentyl glycol and preparating acid and always feed intake the 0.6%(6.56kg of quality in reactor) particle diameter is the diatomite of 75 μm, continue heated and stirred 2h, then heating is stopped, when being cooled to 60 DEG C Deng the temperature of product in still, open the valve at the bottom of still, with refining filtering pump by flow out material pumping in pressure filter, employing order number is that the filter screen of 270 μm carries out circulation press filtration, press filtration material out turns back in reactor, after circulation press filtration carries out four minutes, the color of the product returned has not seen the residual of diatomite particle, product after press filtration being decoloured pours in pail pack.
Above content shows and describes ultimate principle of the present invention and principal character.The technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection domain is defined by appending claims and equivalent thereof.
Claims (8)
1. a preparation technology for amyl-based polyol fatty acid ester, is characterized in that: described preparation technology is the preparating acid be mixed with for the unary fatty acid that the amyl-based polyol of the next present lot of buying is different with several carbonatoms,
First determine the theoretical molar proportioning of carrying out with such preparating acid completely needed for esterification according to amyl-based polyol used or the quantity that mixes hydroxyl in new penta season polyol molecule, or according to former for amyl-based polyol or mix new penta season polyvalent alcohol and the experience mol ratio that formed of such preparating acid select the mol ratio of current lab scale;
Adopt tosic acid as catalyzer, rely on heating to carry out esterification when logical nitrogen, and the water taken out of with nitrogen is collected by collection device, observe in collection device and no longer included after water deviates from 5 ~ 20 minutes, sampling, the acid number of working sample, makes current lab scale sample meet acid number≤1.5mgKOH/g by the adjustment of one or many lab scale mol ratio;
Add adsorption decolouriser, continue heated and stirred 0.5 ~ 2h, then heating is stopped, when being cooled to 50 ~ 70 DEG C in lab scale sample, suction filtration is carried out while hot in the Büchner funnel being covered with middling speed quantitative paper, product in filter flask is transferred in reagent bottle, the method specified according to GB/T7305-2003, measure the separation property of synthesis liquid and water; After if the result display high-speed stirring recorded terminates within three ten minutes left standstill after, the volume of emulsion layer is less than 3mL, then represent that the separation property of this synthesis liquid and water is good, terminate this lab scale;
Acid number≤1.5mgKOH/g in this lab scale and synthesis liquid and water separation property also satisfactory lab scale mol ratio carry out large-scale production as the proportioning raw materials of present lot raw material.
2. the preparation technology of amyl-based polyol fatty acid ester according to claim 1, is characterized in that described concrete steps are as follows:
step S1:the amyl-based polyol of present lot that buying is come and the unary fatty acid of different carbonatoms, first the mixed in molar ratio of unary fatty acids different for several carbonatoms by setting is got up, calculate this mixing acid amount to molecular weight, the quantity calculating amyl-based polyol used or mix hydroxyl in new penta season polyol molecule determines the theoretical molar proportioning of carrying out with such preparating acid completely needed for esterification, according to former for amyl-based polyol or mix new penta season polyvalent alcohol and such preparating acid formed experience mol ratio carry out lab scale test, if the quantity of amounting to hydroxyl of the hydroxyl value of amyl-based polyol used or mixing amyl-based polyol is n, then preparating acid and amyl-based polyol or mix amyl-based polyol theoretical molar than being n,
step S2:set amyl-based polyol in this lab scale or mix new penta season polyvalent alcohol and the mol ratio of preparating acid be 0.9:n ~ 1.3:n;
step S3:carry out lab scale, in the three-necked bottle of 500mL, first put into magnetic stir bar, drop into the preparating acid of 0.4 ~ 2.4mol, then according to the mol ratio that sets in step S2 drop into respective amount amyl-based polyol or mix new penta season polyvalent alcohol, open the intensification switch of oil bath heater, material in still is heated, when temperature in the kettle is raised to 110 ± 4 DEG C, add preparating acid and amyl-based polyol used or mix new penta season polyvalent alcohol always feed intake quality 0.5 ~ 2% tosic acid as catalyzer, under nitrogen tube is inserted into liquid level, nitrogen is passed into the flow velocity of 10 ~ 100mL/min, open the stirring of stirrer in magnetic agitation still, timing from now, material in still is warmed up to 120 ~ 250 DEG C, heating 5 ~ 24h, the water of observing response by-product is deviate to the speed conditions in collection device under the drive of nitrogen, by the time no longer included after a water deviates from collection device in 5 ~ 20 minutes, sampling,
step S4:the acid number of working sample, if the acid number≤1.5mgKOH/g of sample, then leaps to step S9; If the acid number > 1.5mgKOH/g of sample, then enter next step;
step S5:continue reaction 0.5 ~ 2h;
step S6:the reacted acid number of sampling and measuring, if acid number≤1.5mgKOH/g, then jumps to step S9; If acid number > is 1.5mgKOH/g, then enter next step;
step S7:judge the absolute value of acid number and the adjacent last hypo acid value difference measured in above-mentioned steps S6, if this absolute value > is 0.5mgKOH/g, then return step S5; If this absolute value≤0.5mgKOH/g, then enter next step;
step S8:if acid number is > 1.5mgKOH/g still, then terminate this lab scale, and return step S2 again adjust in the scope of 0.9:n ~ 1.3:n and set once amyl-based polyol or mix new penta season polyvalent alcohol and the concrete mol ratio tested of preparating acid lab scale; If acid number≤1.5mgKOH/g, then enter next step;
step S9:in three-necked bottle, add amyl-based polyol used or mix new penta season polyvalent alcohol and preparating acid always feed intake quality 0.5 ~ 5%, particle diameter is the adsorption decolouriser of 65 ~ 80 μm, continue heated and stirred 0.5 ~ 2h, then heating is stopped, when being cooled to 50 ~ 70 DEG C in lab scale sample, in the Büchner funnel being covered with middling speed quantitative paper, carry out suction filtration while hot, the product in filter flask is transferred in reagent bottle;
step S10:according to the method that GB/T7305-2003 specify, synthesis liquid in mensuration reagent bottle and the separation property of water, if be less than 3mL at the volume of the three ten minutes internal emulsification layers left standstill after the result display high-speed stirring recorded terminates, then represent that the separation property of this synthesis liquid and water is good, terminate this lab scale, write down this batch of preparating acid used and the suitable mol ratio of amyl-based polyol, using the mol ratio of this lab scale as proportioning raw materials when carrying out large-scale production with the raw material of present lot; If the separation property of measurement result display synthesis liquid and water is bad, then return step S2
,in the test of fine setting lab scale preparating acid and amyl-based polyol or mix new penta season polyvalent alcohol concrete mol ratio, then carry out lab scale next time;
step S11:large-scale production.
3. the preparation technology of amyl-based polyol fatty acid ester according to claim 1 and 2, is characterized in that the step of described large-scale production is specially:
step S111:the present lot obtained with lab scale amyl-based polyol used or mix new penta season polyvalent alcohol and the mol ratio of preparating acid, at 2M
3reactor in, drop into preparating acid and amyl-based polyol or mix new penta season polyvalent alcohol, the total mass of raw material in still is made to be in the scope of 500 ~ 1500kg, open and stir, during beginning, rotating speed maintains 5 ~ 50rpm, open the heating valve of reactor, material in still is heated, when temperature in the kettle is raised to 115 ± 5 DEG C, add preparating acid and amyl-based polyol used or mix new penta season polyvalent alcohol always feed intake quality 0.5 ~ 2% tosic acid as catalyzer, open nitrogen valve, nitrogen is passed into the flow velocity of 1 ~ 100L/min, the rotating speed of stirring is brought up to 50 ~ 300rpm, timing from now, material in still is warmed up to 120 ~ 250 DEG C, heating 5 ~ 24h, the water of observing response by-product is deviate to the speed conditions in collection device under the drive of nitrogen, by the time no longer included after a water deviates from collection device in 5 ~ 20 minutes, sampling, the acid number of working sample,
step S112:if the acid number of sample can not reach≤level of 1.5mgKOH/g, then carry out reaction 0.5 ~ 2h, resampling detects acid number, until the acid number≤1.5mgKOH/g of sample;
step S113:in reactor, add amyl-based polyol used or mix new penta season polyvalent alcohol and preparating acid always feed intake quality 0.1 ~ 2% adsorption decolouriser, continue heated and stirred 0.5 ~ 3h, then heating is stopped, when being cooled to 50 ~ 70 DEG C Deng the temperature of product in still, open the valve at the bottom of still, with refining filtering pump by flow out material pumping in pressure filter, order number is adopted to be 250 ~ 300 object filter screens, carry out circulation press filtration, press filtration material out turns back in reactor, the color that circulation press filtration proceeds to the product returned do not seen adsorption decolouriser particle residual till, product after press filtration being decoloured pours in pail pack.
4. the preparation technology of amyl-based polyol fatty acid ester according to claim 1 and 2, is characterized in that: described amyl-based polyol or mix new penta season polyvalent alcohol be one or more in ditrimethylolpropane, tetramethylolmethane, dipentaerythritol, neopentyl glycol.
5. the preparation technology of amyl-based polyol fatty acid ester according to claim 3, is characterized in that: described amyl-based polyol or mix new penta season polyvalent alcohol be one or more in ditrimethylolpropane, tetramethylolmethane, dipentaerythritol, neopentyl glycol.
6. the preparation technology of amyl-based polyol fatty acid ester according to claim 2, is characterized in that: described adsorption decolouriser can be gac, atlapulgite, attapulgite, diatomite.
7. the preparation technology of amyl-based polyol fatty acid ester according to claim 3, is characterized in that: described adsorption decolouriser can be gac, atlapulgite, attapulgite, diatomite.
8. the preparation technology of the amyl-based polyol fatty acid ester according to claim 6 or 7, is characterized in that: when described adsorption decolouriser is gac, can use together in conjunction with diatomite, attapulgite, atlapulgite.
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