CN1057645A - The method of separating by-products from technical-grade camphor - Google Patents
The method of separating by-products from technical-grade camphor Download PDFInfo
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- CN1057645A CN1057645A CN 91104319 CN91104319A CN1057645A CN 1057645 A CN1057645 A CN 1057645A CN 91104319 CN91104319 CN 91104319 CN 91104319 A CN91104319 A CN 91104319A CN 1057645 A CN1057645 A CN 1057645A
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- camphor
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- crystallisation process
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
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- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of from the technical-grade camphor of content at least 50% method of removing foreign matter, this method comprises technical-grade camphor is melted, by cooling pure camphor is crystallized out then, after initial crystallisation process is deadlocked subsequently basically, utilize the method for heating for some time to make crystallisation process restart at least again to carry out once.
Description
Reset through firpene by α-Pai Xi, the reaction product that the reactions steps such as catalytic hydrogenation of amphene acetoxylation, isobornyl acetate hydrolysis and iso-borneol prepare the artificial camphor gained contains many disagreeable by products, they belong to usually and contain terpene hydrocarbon (amphene, tricyclene, kautschin and isomer), all kinds of materials of terpenol and terpenone.
In order from this mixture, to obtain camphor, so that the softening agent of nitrocellulose or as the softening agent of cellulose propionate in producing as zylonite and nitrocellulose finish, from crude mixture, isolate camphor with distillation and the method that distils usually.But, if camphor must meet high standard, for example be used for medicine, then these purification process are nowhere near.Here be meant the situation of camphor as for example cardiotonic drug or sanitas (camphor spirit, ointment formulation).In order to meet the purity requirement of purposes defined for this reason in a lot of medicines, must recrystallization be once or secondary again from solvent (mainly being ethanol) with camphor.This has caused solvent again except the trouble of bringing the mother liquor processing additive decrementation also loses camphor and solvent simultaneously, and the finished product need the high-energy drying.
Now be surprised to find that, if without solvent recrystallization, but from melt with the technical-grade camphor crystallization, then these shortcomings can be avoided.But must meet some requirements.If only carry out recrystallization with the method that continues cold fuse-element, in fact crystallization is deadlocked soon after isolating a part of crystallization camphor.The present invention relates to a kind ofly be at least the method for removing foreign matter 50% the technical-grade camphor from content, this method comprises technical-grade camphor is melted, utilize cooling that pure camphor is crystallized out then, after initial crystallisation process pauses subsequently basically, by heating for some time, make crystallisation process restart at least again to carry out once.
So with the technical-grade camphor fusing, cooling begins to crystallize out up to pure camphor then.Preferably in preliminary experiment, measure the fusing point of the technical-grade camphor of wanting purifying earlier, when can melt fully, when can begin crystallization during cooling so that can know technical-grade camphor.Continue cooling up to there being a large amount of camphor to crystallize out again.When about 30% to 50% weight of contained camphor has crystallized out; crystallisation process is deadlocked usually basically; promptly; it is very slow that crystallization becomes; so that it is meaningless as the industrial purification process; according to the present invention, with mixture heating up so that crystallisation process restart, but the major part of the pure camphor that goes out of crystallization no longer melts.In general, raise about 2 to 5 ℃ and to keep 3-10 minute be suitable for reaching this purpose heating.Also might in Glass Containers, carry out the preparation property test to determine to be suitable for most the temperature and the time length of used technical-grade camphor.In case begin crystallization once more, then stop to heat and continue once more cooling up to there being a large amount of camphor to crystallize out again.After crystallisation process pauses once more basically, can finish crystallisation process or begin crystallisation process once more by another short period of time heating.In general, repeat crystallisation process one to four time by of short duration heating; Preferably only carry out once or twice, especially when the purity of emphasizing crystallization camphor will be very high, the situation of medical camphor for example, because along with attempting camphor to be crystallized out quantitatively or substantially quantitatively and carry out the increase of crystalline number of times, some impurity can become solid danger equally and also increase.
By means of method of the present invention, the melt of technical-grade camphor might be changed into adhesive aggregation, porous crystallization block, wherein impurity exists with liquid form, also have remaining camphor more or less to exist with liquid form simultaneously, this depends on when crystallisation process stops.Through opening the bottom of crystallisation vessel subsequently, and elevated temperature (about usually 2-5 ℃) slightly, so liquid impurity and be that the residual camphor of liquid might drip from the crystallization camphor of adhesive aggregation and oozes equally.If used technical-grade camphor is very impure or require final product pure especially, then can repeat purge process of the present invention where necessary.But just as mentioned above, under a lot of situations, even as medical camphor, it is just enough to carry out single step purification, that is, the crystallisation process that restarts by of short duration heating preferably is limited in once or twice no more than.
In order to obtain the productive rate of maximum possible, most convenient be that the residual solution that contains a large amount of impurity that will obtain in crystallisation process is done distillation and handled, sublimate generally contains the above camphor of 60% weight, and it is recycled to according in the crystallisation process of the present invention.
Can in tubular drip type crystallizer, carry out still according to purification process of the present invention, described in (1982) 148 pages of the 4th edition the 6th volumes of " Chemische Technologie " (" chemical technology ") of WinnacKer-K chler, or described in the application's embodiment 2, use cooling worm, or as United States Patent (USP) 3, carry out with dynamical fashion in the device of mentioning in 621,664.
The camphor of purifying is important product.In the production of zylonite and nitrocellulose finish it be nitrocellulose can't displaced softening agent.Verified it can also be used to the plasticising cellulose propionate, camphor also can be used to compounding pharmaceutical preparation (for example as camphor spirit), as perfume composition, as odor improvers, and as the anti-cysticercus agent of clothes.It can also be used to producing smokeless powder and detonator.Another important application of camphor is the perfume compound that celebration is used as ceremony.Following examples have illustrated the method according to this invention.Percentage composition among each embodiment is weight percentage.Said cooling and Heating temperature all refer to the cooling of thermostatic bath or the temperature of heating medium.
Embodiment 1
312.5 gram technical-grade camphors (purity is 89.4% weight) are added in the tubular crystallizer with solid form, and the heating and cooling chuck of crystallizer links to each other with thermostatic bath, and camphor is fusing fully under 180 ℃ Heating temperature.Under the atmosphere that always has inert nitrogen, make uniform melt carry out crystallization by following cooling and heating schedule, up to being solidified into the porous block:
-in 30 minutes, be cooled to 167 ℃ by 180 ℃
-in 4 minutes, be heated to 170 ℃ by 167 ℃
-in 30 minutes, be cooled to 165 ℃ by 170 ℃
-in 5 minutes, be heated to 168 ℃ by 165 ℃
-in 60 minutes, be cooled to 161 ℃ by 168 ℃
-in 4 minutes, be heated to 165 ℃ by 161 ℃
-in 120 minutes, be cooled to 151.5 ℃ by 165 ℃
Crystallisation process is opened bottom valve after finishing, and collects the remaining melt of 44 grams, and wherein camphor content is 51.3%(weight).Then, the temperature of heating medium was elevated to 160 ℃ by 151.5 ℃ in 18 hours, oozes 52 gram camphor fractions, wherein the weight content of camphor is 90.3%, and is last, will remain in the crystal melting in the device and separates.The camphor amount that purifying is good is 216 grams, and purity is 97%(weight).
Embodiment 2
As described in embodiment 1,152.1 gram technical-grade camphors (purity 84.2% weight) are added in the tubular crystallizer fusing fully under 180 ℃ of Heating temperatures with solid form.Under the atmosphere that always has inert argon, evenly adding a small amount of camphor crystal as crystal seed in the melt, and making melt carry out crystallization by following program, be solidified into the porous block thing up to melt:
-in 120 minutes, be cooled to 129 ℃ by 156 ℃
-in 5 minutes, be heated to 132 ℃ by 129 ℃
-in 120 minutes, be cooled to 122 ℃ by 132 ℃
-in 4 minutes, be heated to 126 ℃ by 122 ℃
-in 120 minutes, be cooled to 116 ℃ by 126 ℃
After crystallisation process finishes, open the bottom valve of crystallizer, the temperature of heating medium was elevated to 135 ℃ by 116 ℃ in 25 hours.Collect camphor content and account for 78.5% fraction 71 grams.Then, will be retained in the crystal melting in the device and separate.The camphor amount that purifying is good is 80 grams, and purity is 90%(weight).The crystal that obtains by this way can further improve camphor content by crystallization once more.
Embodiment 3
Double centner camphor (content 89.4%) is joined in the crystallizer with solid form; crystallizer is made of stainless steel vessel; peripheral all adiabatic; it is of a size of long 600 millimeters; wide 600 millimeters, high 700 millimeters, inside is equipped with 4 inches heat exchange thermosistors of the coil form that four heating and cooling use; oil is by wherein flowing through, and camphor is the fusing fully under 185 ℃ of protection gas with the argon gas.Then, make even melt crystallization by following cooling and heating schedule with thermostatic bath, up to being solidified into the porous block:
-be cooled to 167 ℃ (speed: 1.8 ℃/minute) by 185 ℃
-be cooled to 161 ℃ (speed: 0.1 ℃/minute) by 167 ℃
-be heated to 164 ℃ (speed: 0.5 ℃/minute) by 161 ℃
-be cooled to 157 ℃ (speed: 0.1 ℃/minute) by 164 ℃
-be heated to 160 ℃ (speed: 0.5 ℃/minute) by 157 ℃
-be cooled to 155 ℃ (speed: 0.1 ℃/minute) by 160 ℃
When internal temperature is 155 ℃, open the crystallizer bottom discharge valve that heats down at 185 ℃, emit 125 kilograms liquid fraction (camphor content 70.5%).Then, keep baiting valve to open, with the rate of heating of 0.1 ℃ of per minute temperature is brought up to 161 ℃ (liquid oozes process) by 155 ℃, flow out 10 kilogram of second fraction (camphor content 93%), it can directly be used in next batch of material again.At last, close bleeder valve in the time of 161 ℃, the solid camphor of staying in the crystallizer melts fully at 185 ℃.The result obtains 65 kilograms of purity 96.1%(weight) purifying camphor.
Claims (4)
1, a kind ofly is at least the method for removing foreign matter 50% the technical-grade camphor from content, this method comprises technical-grade camphor is melted, utilize cooling that pure camphor is crystallized out then, after initial crystallisation process is deadlocked subsequently basically, method with heating for some time makes crystallisation process restart at least to carry out once again.
2, the process of claim 1 wherein with the heating for some time method make crystallization restart again to carry out 1 to 4 time.
3, claim 1 and 2 method, wherein the content of technical-grade camphor is 80 to 95%(weight).
4, a certain method in the claim 1 to 3 wherein, distils the resistates that obtains in the crystallisation process, and the sublimate of gained is recycled to according in the process of the present invention.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19904020855 DE4020855A1 (en) | 1990-06-29 | 1990-06-29 | Purifying technical grade camphor prodn. - by melt crystallisation with at least one reheating step once initial crystallisation has ceased |
| DEP4020855.9 | 1990-06-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1057645A true CN1057645A (en) | 1992-01-08 |
Family
ID=6409410
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91104319 Pending CN1057645A (en) | 1990-06-29 | 1991-06-28 | The method of separating by-products from technical-grade camphor |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN1057645A (en) |
| DE (1) | DE4020855A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101869601A (en) * | 2010-06-28 | 2010-10-27 | 潘冠军 | External veterinary medicament |
-
1990
- 1990-06-29 DE DE19904020855 patent/DE4020855A1/en not_active Withdrawn
-
1991
- 1991-06-28 CN CN 91104319 patent/CN1057645A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101869601A (en) * | 2010-06-28 | 2010-10-27 | 潘冠军 | External veterinary medicament |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4020855A1 (en) | 1992-01-02 |
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| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |