CN1070164C - Pinene esterifying and saponifying process synthesizing borneol and composite boron-titanium based catalyst - Google Patents

Abstract

In the forest product chemical industry, synthesized borneol mainly made from turpentine and oxalic acid dihydrate contains about 40% of isoborneol and results in drug effect and fragrance both below those of natural products. In the process of the existing catalytic esterification method of making borneol, oxalic acid dihydrate and alkali are consumed in an unreasonable way, finally not compounded to finished products or byproducts but discharged to external environment. The process flow of the present invention can reduce the consumption of oxalic acid dihydrate and alkali to the minimum limit. A specific component BTiG-95 catalyst in the present invention can make partial finished products have borneol content over 80%, closely similar to that in natural products.

Description

Pinene esterifying and saponifying process synthesizing borneol and composite boron-titanium based catalyst

Borneol, the popular name borneol is a kind of dicyclo terpene alcohol on the structure, so also claim embedding alcohol.It is a kind of famous and precious Chinese medicine, also is a kind of banksia rose type spices, but it is this for the resource of gathering to have only the only a few plant to have, and having invented then with turps is starting raw material, the Technology of synthetic borneol.Turps is the terpene blend based on α-Pai Xi and beta-pinene that extract from rosin, and wide material sources are reliable, utilizes it to produce borneolum syntheticum certainly selecting of a kind of good intelligence really.Domestic priority has ten many enterprises to produce synthetic borneol, and they mostly are woodsization factory and synthetic perfume factory.From technical elements, correct ownership should be chemistry of forest product industry.

1886, scientist can use turps synthetic borneol.Since century, the chemist constantly explores the new way of borneolum syntheticum more than one, and that had explored has: the enzyme transforming process of acidic catalyst esterification-saponification method, firpene and the Terpineol 350 of camphor reduction method, firpene, the direct hydration method of α-Pai Xi etc.

These 80 years in generation of world, the α-Pai Xi direct hydration method that with a large amount of mordenites is catalyzer is at first released application in zhuzhou, hunan province woodsization factory, then again in the factory of 50 tons of the newly-built annual outputs of Yunnan Province's Simao City, carry out plant-scale big production, through the check of running and social practice in a few years, because of can not pass to be forced, cost stopped production eventually.This process explanation: though the quality of hydration method borneolum syntheticum can reach natural product high level like that fully, it has only learning value, and can't produce economic benefit in industrial practice.At present, be able to take industrial production screening and test and be the acidic catalyst fatization-saponification method of firpene in the method for using still, used an acidic catalyst mainly contains two kinds of canopy acid anhydride and metatitanic acids.In addition, other has a kind of GIC-90 solid acid catalyst to release application [1], but also will just can make corresponding conclusion after after a while.

The catalytic advantage of boric anhydride is that facility investment is little, and esterification time is short, and is lower to the purity requirement of oxalic acid, and in the process of implementing the oxalic acid recovery, removal of impurities and recrystallization are much easier.Shortcoming is that esterification efficient is low, acutely makes the difficulty of operation control bigger because of the esterification heat release again.The explosion hazard that repeatedly causes has thus taken place in China, and also causing of having, workman's on duty was unfortunate dead.The esterification efficiency ratio boric anhydride of metatitanic acid catalyzer will exceed 6-10 percentage point, reacts also more steady safety, also only flash can take place and towards the material accident even esterification control is improper, and the accident tendency occurs early, and sign is also fairly obvious.In case take place also only towards not quick-fried, so do not hindered remarkable so far.Shortcoming is to high slightly to equipment requirements, and is also high to the purity requirement of oxalic acid except that corresponding the wanting the height of consumption of prescription mesoxalic acid, thereby just can only require as strict as possible the recovery and the reuse of oxalic acid.

Boric anhydride has been used over half a century.Metatitanic acid from camphor production by simplifying the operation, change corresponding physical and chemical index, graft application is on borneol production, also have 16 years enough, after jiangsu wuxi China trade chemical company at first takes metatitanic acid catalysis, Zhejiang is pure will wait several factories sequential use so far for having of continuing, and lasts also short.

From documents and materials, the effect of [1] GIC-90 solid acid catalyst is compared very approaching with metatitanic acid, but the advantage that it has opposing to poison, and it is progressive and developing things, and all remain outcome from now on.

Yellow sticky polymkeric substance in the boric anhydride Catalytic processes byproduct is more, is called heavy oil in this yellow oil factory, and quantity accounts for 30～40% of turps input amount, and its price is lower.The foreshot of reactant is water white organic mixture, is called white light oil in the factory, and this also is its byproduct, but quantity has only about 10% of turps input amount.White light oil price is than heavy oil height.The byproduct quantity of metatitanic acid Catalytic processes is opposite with boric anhydride just, heavy oil only accounts for 10～15% of turps charging capacity, white light oil is about 2.5 times of heavy oil, in white light oil, also contain the kautschin about 30%, just can obtain a kind of industrial chemicals suitable with the turps price as if it is separated.From the value of byproduct, also good not as metatitanic acid of boric anhydride.

Though the overall advantage of the titanium catalyst that rise the back exists, do not reach the level that increases substantially, and will implement it, again because of high slightly must the adding of the requirement of equipment invested, this just long-established enterprise can not make a decision and abandon boric anhydride and use its cause instead.Be the two at present and deposit neat act, all measures of in production management, taking some to maximize favourable factors and minimize unfavourable ones, thus obtain actual benefit.

Borneol can find in multiple natural essential oil, and its isomer isocamphol is rarely found at occurring in nature.These two kinds of alcohol all have the pine fragrance of strong happiness, but the price of isocamphol is wanted considerably cheaper on the market, and it is the intermediate that camphor is produced.Because it is cheap, so be large in number and widely distributed in application facet, its acetic ester is progressively replacing the acetic ester of borneol.Just biochemistry medical aspect, borneol just has status and the effect of not replacing.

In the face of the raising of isocamphol production level, borneol production must further be fallen originally and be increased income, and this has been task too impatient to wait.Seek better borneol synthetic method, in medicine, the work of spices Study on Technology, never stopped.

Purpose of the present invention also is in order to realize this target: try to achieve better borneol synthesis technique, try to achieve better catalyzer.The alleged novel method of the present invention is exactly a kind of new borneol production method that can reach above-mentioned requirements, and composite boron-titanium based catalyst then is a kind of more effective borneol synthetic catalyst.For the purpose of making reading conveniently, this just abbreviates composite boron-titanium based catalyst as the boron titanium catalyst hereinafter.

From academic viewpoint, the boron titanium catalyst is the more excellent catalyzer of making by the reasonable combination of Ti, B and other negative ions of performance, and it has the advantage that boric anhydride is difficult for poisoning and metatitanic acid highly effective and safe, can collect the length of the two, restrains the two weak point.From the characteristic that raw catalyst had, conclude technological process and operation rules such as safer esterification more efficiently again, make it to reach more practical more perfect condition.

The present invention's being transplanted in the industrial production progressively gone, to reach the dual purpose that technical progress and benefit improve.

Technical scheme of the present invention is to select best example to formulate for foundation in experimental data base.

Chemical industry even the trial-production of catalyzer has theoretical elaboration and guidance, still is the arduousness work based on experiment even to this day.The boron titanium catalyst also is to produce in such experience, it is one is the composite catalyst that basic raw material is made with industrial metatitanic acid and industrial boric acid, from experiment, learn at present, boric anhydride and titanium catalyst that the effect of this composite catalyst is made than their independent utilizations are much better, with what kind of its good effect of technological operation performance have also understood.Just its reaction mechanism also is in the preliminary stage of inferring to some extent, and not exclusively understands.Be its existing practicality, academic demonstration also waits perfect.

The making method of raw catalyst is as follows:

1, the intermediate hydrous titanium oxide H of tool manufacture titanium dioxide ₂TiO ₃Even centrifuge dripping also can residual dilute sulphuric acid down.Must the washing secondary, as much as possiblely remove it.

2, add 15% NaOH solution while stirring, make PH 〉=9 of suspension liquid.

3, standing over night makes it precipitation.Siphonage is removed supernatant liquid.Add washing and wash secondary, all remove the upper strata clear water at every turn with siphonage.

4, add HCl solution, make PH=4～5, the precipitation of spending the night, siphon dewaters.

In this operation steps, also to turn over and be added with washing and eliminate and detect the pH value of suspension liquid, find that pH value raises then to mend some dilute hydrochloric acid slightly that its pH value of make suring remains between 4～4 always.Want siphon to dewater after the clarification, make suring adds the Na that alkali forms ₂SO ₄Till adding NaCl that acid forms and removing substantially.

The degree of removing of two kinds of sodium salts can be with the Na of one of them ₂SO ₄Unify representative.Measuring method is supernatant liquid to be taken out add equal-volume 10%BaCl ₂The solution shaking makes even, watches its muddy degree quietly.Its opacity be no more than made standard specimen be qualified.Titanium catalyst is very high to the requirement of desalination, otherwise its effect just obviously descends.This desalinization of soil by flooding or leaching requires much lower with regard to the making of boron titanium catalyst, therefore, gives in the correlated standard specimen, can be BaSO ₄Content improve.

5, centrifuge dripping will add the water washing therebetween once in whizzer.

6, the metatitanic acid of take out cleaning comes, and puts into 100 liter enamel stills, add water a little, stir pulping.

7, make metaboric acid iron precipitation, it will use as recombiner together with its mother liquor.

The generating principle of metaboric acid iron is as follows:

8, the suspension liquid of metaboric acid iron is added in the 100 liter enamel stills stir.

So far thing clearly in the boron titanium catalyst, except metatitanic acid iron, still has the composition of NaCl, and its katalysis is insensitive to salt residue to be exactly the thing in the reason.

9, open steam material in the still boil resemble the dough shape till.

10, take out the moistening catalyzer of xanchromatic, morsel is put into oven for drying.Its temperature is 110 ℃～130 ℃ bakings 4 hours, and 130 ℃～150 ℃ were dried by the fire 3 hours.

11, take out stiff bulk catalyst, put into the cylinder ball mill pulverizing that steel ball is housed.

12, the catalyst seal that is milled into powder is wired up, in order to using.

The making of boron titanium catalyst is compared with the making of titanium catalyst, and except that not adding metaboric acid iron and mother liquor thereof, all the other are all equally handled.Titanium catalyst is effective ingredient H at last ₂TiO ₃With invalid element TiO ₂Mixture, and the boron titanium catalyst has been owing to added other three kinds of materials, its composition is just complicated, but can judge according to making 7: it is with H ₂TiO ₃And TiO ₂Be main, with a spot of Fe (BO ₂) ₃With NaCl be the mixture of assisting.To H ₂TiO ₃The amount of mixing sodium metaborate and iron(ic) chloride mixed solution in the paste is changeable, and concrete can treat respectively according to other difference of places of origin of raw materials level.For the purpose of convenient,, select H for use by each thing mixed ratio relation of making in 7 equation to the expression of mixing ₃BO ₃Incorporation as table note of the ancient Chinese of the total mass of all mixing, H is only remembered in the doping in the table later on ₃BO ₃Incorporation, other then can know by inference by it.Adopt H ₃BO ₃Another benefit of calculating is to make to detect and trouble that various conversions are exempted in the technology supervision, and this is that detection because of the B element can make it to become behind the boric acid and knows, so the effect of knowing has at a glance just been arranged.In the process of making the boron titanium catalyst, be not unique selection with iron(ic) chloride yet, Fe ₂(SO ₄) ₃Also can, AlCl ₃, CrCl ₃Wait other acid metal salt good, only with FeCl ₃6H ₂This water purification agent of O is the most cheap and easy to get.Use FeCl ₃Another benefit be to reduce the material requirement of equipment, most containers can be made with the soft steel of cheapness.

The boron titanium catalyst is also continued to use the catalyzer esterification---and the saponified traditional process is made borneol, but its catalysis characteristics and B ₂O ₃And H ₂TiO ₃Be different.It has following characteristics:

1, in different esterification temperature-rise periods, carries out esterification with same starting material with same catalyzer, different reaction preference and different product yields can occur.Table 1 is H ₃BO ₃Incorporation accounts for the boron titanium catalyst of catalyzer total mass 2.5%, be synthetic starting raw material with pinus khasys rectified oil of turpentine (α-Pai Xi content reaches 96%), feed ratio is: turps: anhydrous oxalic acid (80 orders sieve, water content≤0.2%): catalyzer=200g: 50g: 8g, the data that experimentize and get.The data of numbering 1,2 show that the yield of boron titanium catalyst improves than the production actual recovery of using titanium catalyst enterprise is existing.

Table 1

Numbering	Esterification temperature-rise period (reactant temperature indicating)	Thick borneol 9	Yield %	Thick borneol composition %					Borneol isocamphol=%
										Water	Sweet fennel oil	Other	Isocamphol	Borneol
				1	90 ℃ ± 2 ℃ totally seven hours half an hour of 55 ℃ ± 2 ℃ 2.5 hours 60 ℃ ± 2 ℃ 1 hour 65 ℃ ± 2 ℃ 1 hour 70 ℃ ± 2 ℃ 1 hour 80 ℃ ± 2 ℃ half an hour, 50 ℃-55 ℃ half an hour	123	61.5	8.5							12.5	1.4	33.5	44	56.7
2	121	60.5	8.5						13	1.6	32.3	44.6	58
				3		45 ℃-50 ℃ 1 hour 50 ℃～55 ℃ 2 hours 55 ℃～60 ℃ 2.5 hours 60 ℃～65 ℃ 1.5 hours 65 ℃～70 ℃ 1.5 hours 70 ℃～80 ℃ 0.75 hour 80 ℃～90 ℃ 0.5 hour totally nine hours 45 minutes	106.5	53.25						8.5	14.7	1.6	26.32	48.88	65
4	108.4	54.2	8.5		14.3				1.8	26.6	48.8	64.7

2, same starting material and material proportion, same esterification temperature-rise period.As long as make the compositely proportional difference of boron titanium catalyst, just have the technological effect that differs widely.Table 2 has just illustrated this situation:

Table 2

Numbering	Esterification temperature-rise period (reactant temperature indicating)	H 3BO 3Mix %	Thick borneol 9	Yield %	Thick borneol composition %					Borneol isocamphol=%
											Water	Sweet fennel oil	Other	Isocamphol	Borneol
					1	90 ℃ ± 2 ℃ totally seven hours half an hour of 55 ℃ ± 2 ℃ 2.5 hours 60 ℃ ± 2 ℃ 1 hour 65 ℃ ± 2 ℃ 1 hour 70 ℃ ± 2 ℃ 1 hour 80 ℃ ± 2 ℃ half an hour, 50 ℃-55 ℃ half an hour	2.5	122	61							8.5	12.75	1.5	32.95	44.3	57.35
2	4	87	43.5	8.5						15.7	1.1	21.4	53.3	71.35
					3		5	76	38						8.5	16.5	0.5	16.4	58.1	78

Numbering every data of 5 are the mean value of numbering every corresponding data of 1,2 in the table 1 in the table 2, and the charge ratio of numbering 6,7 also is: turps: anhydrous oxalic acid: catalyzer=200g: 50g: 8g, and raw materials used used identical with table 1 experiment.From the data of table 2 as can be seen: the addition of recombiner is not The more the better yet, and it only is only useful in limited scope.

The quality of Pinus kesiya Royle ex Gord. Var. Langbianensis (A. Chev.) Gaussen oil is classic, but it only originates in Yunnan Simao Diqu one band.The turps that gets from other seeds of other region will differ from certainly.H in table 1, the table 2 ₃BO ₃The good good data that incorporation 2.5% draws all are for using the pinus khasys fuel-economizing, the turps in other place of production just should indiscriminately imitating of machinery not being applied mechanically.The present invention can't analyze one by one and test again the turps of domestic and international various places.Therefore, for the purpose of seriously, every kind of turps drops into before the industrial application, should select 1.5%, 2%, 2.5%, 3% H respectively for use ₃BO ₃Incorporation is made the boron titanium catalyst, makes certainly by lab scale and selecting.With the corresponding theoretical direction science and technology test of coordinating and seeking out best collocation, the conclusion with the science and technology test instructs industrialized behave again, is only the safest method.

The boron titanium catalyst is not afraid of NaCl and NaSO ₄Infringement also by experiment confirm, add the pulverous NaSO of 0.25 gram in the 50 gram anhydrous oxalic acids ₄, grind mixing, it is fed intake to use do not find detrimentally affect, this just makes the oxalic acid recovery operation more convenient.In addition, because its catalytic performance is safe and reliable, utilization prolongs the measure in reaction times a little just can make the volume of esterifying kettle expand 2 cubic metres to, and labor force on duty also just can correspondingly reduce.

Although the boron titanium catalyst has the B of being better than ₂O ₃And H ₂TiO ₃Performance, but upright the going of arc treat and advocate it, enterprise perhaps can be because of fearing that changing the place fluctuation overall situation is reluctant to repay examination, just as continued to use B in the past always ₂O ₃The attitude that the long-established enterprise of catalyzer treats titanium catalyst is the same.From academic viewpoint, it still is a part in the whole manufacture method of esterifying and saponifying borneolum syntheticum.If its integral part as a new firpene borneolum syntheticum method, its value just is the sub-fraction in the novel method overall gain, adopts it and can cause a series of favourable chain reactions, and people will be more deep therefrom to its understanding.

This pinene esterifying and saponifying process synthesizing borneol that contains the boron titanium catalyst exists, and its particular content can clearly be showed by Fig. 1.Seen after this figure, also just understand it with the different places of current technology [2].By contrast, novel method has three tangible advantages, and these advantages not only front and back perforation join together, also can discretely come, and use separately.This is existing B also just ₂O ₃Catalysis and H ₂TiO ₃Catalytic local improvement provides scientific basis.Now these advantages are illustrated in down:

1, the improvement of alkaline hydrolysis saponification aspect:

No matter current is to use B ₂O ₃Catalytic esterification is still used H ₂TiO ₃Catalytic esterification, the alkaline hydrolysis of the oxalic acid borneol acetate that they obtain and saponification all are to finish with the solution of NaOH, and the former directly uses 30% industrial lye, and the latter then water waters down to 8～10%.NaOH is consumed after participating in reaction.And in this law, be 10% the NaOH solution except that adding excessive slightly concentration, need add Ca (OH) ₂Fine powder earlier by NaOH and the effect of oxalic acid borneol acetate, becomes borneol and sodium oxalate, sodium oxalate in the aqueous solution with Ca (OH) ₂Effect reverts back to NaOH again, reacts as follows:

After reaction was finished, the initial 2NaOH that adds just obtained regeneration therefrom.

From top reaction formula also as can be seen: Ca (OH) ₂Coupling is the proportionlity of a molecular weight to two molecular weight in the application quantity of NaOH.Ca (OH) ₂As long as application quantity meet this requirement, then infer theoretically, all sodium hydroxide be can holomorphosis as before, promptly in reaction, only consume Ca (OH) ₂, do not consume NaOH, from D22 to E22, turn back to D22 from E22 again, can unlimited circulation go down.Can not be such but be actually, in the application repeatedly that goes round and begins again, always have some artificial waste, must want some an amount of replenishing, but this can give supply more slightly after the utilization several times.This saving has great economic worth.

H ₂TiO ₃The basically identical of the composition of the reaction oil of catalysis gained and boron titanium catalysis gained is applied mechanically this law without any problem.

B ₂O ₃The reaction oil color of catalysis gained is dark, and viscosity is big, and wherein heavy oil is more than 3 times of white light oil, it is also just short that the time of white light oil is taken off in steaming, saponification is directly to carry out with 30% sodium hydroxide industrial lye, obviously does like this volume of equipment is reduced, and saves facility investment.But breadboard lab scale proves, if constant with the alkali total amount, add water concentration is dropped between 10～15%, then Ca (OH) ₂Also add in the lump and carry out the alkaline hydrolysis saponification, also can receive same good effect.

Necessary to Ca (OH) ₂Specification of quality make a brief description, because this is the quantitative irreversible reaction of dissolving the ester class, can't produce adverse influence so calcium hydroxide has a little impurity, can make the calcium hydroxide powder with industrial calcium oxide fully, lab scale also is this powder of usefulness, and effect is fine.If but this unslaked lime of necessarily grilling thoroughly.If burn not saturating, have sandwich or the folder words just can not use.Because when it dissolves into calcium hydroxide, because of burning not saturating and remaining many so little CaCO as vegetable seeds ₃Can not resolve into powder, it is with Ca (OH) ₂Have only appearance one deck to transform after adding together, its reaction is:

Caoxalate is attached to CaCO ₃Particulate surface, its deep inside still are Wingdale CaCO ₃, yellow soda ash then dissolves in the alkaline solution and has gone.Clearly, 2NaOH has originally become Na ₂CO ₃, its accumulation gradually can make concentration of lye reduce and influence the saponification effect.The more disadvantageously CaCO of granule interior ₃In oxalic acid removal process after this, can be by vitriolic strong solution pyrolytic decomposition, a large amount of CO overflow ₂Come, cause the flash accident.

Therefore, used unslaked lime should be the industrial block lime that does not have carbonate, dissolves the application of sieving behind the powdered with a small amount of boiling water again.

2, oxalic acid reclaims the major progress of technology:

It is a great problem of puzzlement borneol factory that oxalic acid reclaims always, and theoretically, the oxalic acid molecule has only its H ⁺Therefore and very simple and easy as if played the guiding addition, till to the last finished product changed into, oxalate denominationby never joined in the borneol molecule and goes, reclaim it also with regard to, but in fact and be not easy.Talk clearly this point and will illustrate earlier where oxalic acid is lost: first place, the invisible waste when two crystal water are taken off in the oxalic acid baking.Second place, B ₂O ₃Catalysis gained reaction oil wants hot water to wash three times, could move into after wash water PH 〉=3 to go in the iron ware to steam to take off white light oil.Three wash waters and steamed white light oil after end water all contain oxalic acid, discharge these waste water and also just the oxalic acid that is dissolved in wherein drained together.The 3rd place, most oxalic acid and firpene esterification are ester compounds such as oxalic acid borneol acetate, have after this become the sodium salt of oxalic acid in alkaline hydrolysis.The one the second is that concentration is low, bulky waste gas waste water, and factory is reluctant that great amount of investment goes to reclaim, and has only the 3rd to be recycle object now.By sodium oxalate system oxalic acid is that CO and NaOH are the last part technology that starting raw material is made oxalic acid, originally can apply mechanically easily, but because the heavy oil that firpene aggregates in responding is mixed in wherein, the thing complexity that just becomes has been got up.Current now recovery technology is: tell remaining alkali lye from still kettle, logical steam extrudes the mixture dilute sulphuric acid thermal degradation of heavy oil and sodium oxalate, and heavy oil is removed.Sodium oxalate can only be made solution step by step because of solubleness is very little, and the sodium oxalate solution pH value with the residual alkali lye adjusting acidolysis of telling makes it to become PH=6 by PH＜1, and residual alkali lye just adds with industrial lye inadequately.The sodium oxalate aqueous solution enters splendid attire PbSO ₄The container of powder stirs conversion.

Because sodium oxalate solubleness is low, so (C in its saturated solution ₂O ₄) ^--Ion is also very rare, once transforms and far can not make all PbSO ₄Become lead oxalate, can only contain Na changing ₂SO ₄Waste water release, irritate sodium oxalate solution again and enter to transform, a secondary like this, even 6～7 times, PbSO make sures ₄All be converted into PbC ₂O ₄Till.With 100 ℃ of acidolysis PbC of 60% sulphuric acid soln ₂O ₄

Take advantage of thermal separation to go out that lead sulfate and bisulphate are plumbous to be come, the oxalic acid Crystallization Separation is come out after the solution cooling again, this process is tediously long tired multiple, and recvery facility and container are many and huge.Untie the adherend of heavy oil sodium oxalate earlier with sulfuric acid, will go neutralize excessive acid, again and again inefficiency with alkali again.Though plumbous vitriol still can be used repeatedly, always contain Pb in each wash water of discharging after washing ⁺⁺Positively charged ion, from the angle of environmental protection, using sulfated lead is not perfect behave.The aforesaid method investment is big in a word, and yield is low, and is of poor benefits.Remove indivedual producers such as chemical plant, Huangpu, Guangzhou and still adhere to making a silk purse out of a sow's ear, reclaim the oxalic acid guard ring overseas, all the other producers fall after rise and recovery system damages and just is reluctant later that great amount of investment gone down again in the oxalic acid price, and recovery operation has also been shelved at this point.The recycling engineering of zhuzhou,hunan woodsization factory is exactly the representative instance of this situation.The not good meeting of oxalic acid quality then is afraid of to reclaim by Wuxi China trade chemical company influence H ₂TiO ₃Catalytic effect, do not give recovery so far always.

Based on above-mentioned certain situation, oxalic acid consumption comes after the turps in the borneol production cost always, has occupied second largest position, produces one ton of borneol and will consume oxalic acid about one ton.Conversion process of the present invention in saponification with steam with water vapour in the process of borneol and finished in the lump, need not numerous and jumbled outside converting apparatus.If what esterification was used is boron titanium catalyst or titanium catalyst, the gained reaction oil can be put into the enamel still without washing and remove to add water and steam and take off white light oil.Facts have proved, need not worry that it can acidolysis.Not washing does not just have waste acid water to produce, moreover because the heavy oil that these two kinds of catalyzer produce is less, so the shared ratio of the heavy oil in the oxalic acid borneol acetate is also little, need only release to wash to eliminate with the white waste acid water that steams white light oil rear lower and steam residue remaining behind the thick borneol, caoxalate and heavy oil in the slag are separated, must be mixed with TiO in the gained caoxalate ₂And H ₂TiO ₃Solid matter, but they do not influence later reaction and recovery.Whole process does not all have the loss of oxalic acid water, and the oxalic acid in all waste acid waters all enrichment is that caoxalate has been left, and is reclaimed thereby merge together.If be B ₂O ₃The reaction oil of catalysis gained, also available caustic soda white lime associating saponification, though its gained also is the mixture of caoxalate and heavy oil, but wherein the content of heavy oil is just many, separately with washing ester and the acid waste water that comes to go to decompose be not reach to make the two purpose of separating, must go with the sulphuric acid soln of 10-15% to decompose.At normal temperatures, this acid concentration is safe to the oxalic acid of separating, and sulphuric acid soln is supply and using repeatedly slightly also, and this is a very easy local technical reform scheme.

Fig. 2 is a process flow sheet of caoxalate being made first oxalic acid, and it shows understands that applicable industry sulfuric acid and general industry water go to decompose the course that caoxalate obtains oxalic acid.When adding the water heating for dissolving first, thick oxalic acid adds an amount of BaCO ₃Be very necessary, this can remove the SO that is mixed in the oxalic acid ₄ ^--Ion reduces the crystallization number of times.Use after the boron titanium catalyst, because it has the ability that prevents salt poisoning, so used oxalic acid and do not require it is the top grade product.But, therefore any recovery specification of quality can not proposed from the position of production management.Facts have proved that recovery article content 〉=99% is fully harmless concerning result of use.

Fig. 3 is the mechanical flow digram that secondary and later caoxalate are made oxalic acid, the supply of the vitriol oil and BaCO ₃Interpolation constant, and mother liquor just returns the past as the solvent of work in-process oxalic acid, does like this and can save many operational troubles.Mother liquor can not infinitely use, otherwise 99% content does not just guarantee that after the several times, all three kinds of mother liquors are all used Ca (OH) ₂The neutralization clarification, the gained caoxalate can be sent hydrolysis procedure back to and directly be used.

This law only consumes cheap sulfuric acid, the high value oxalic acid that output is share.The result of lab scale proves, gained oxalic acid is about 70% of charging capacity, simple and direct again recovery technology also bothers manyly than purchase, do recovery and also increased many organize content than not doing to reclaim, corresponding recovery production management is the key point of yield benefit height, should treat the same crucial status that is placed on of the scientific and technological achievement of it and this.

3, replace the oily brain in the current technology to steam work again with the hot water washing oil, [2], the labour has saved, and benefit has also improved.

The adrip solid water borneol E1 that from the distillation collector, takes out, when centrifugal water dumping purifies water substantially, go to wash with 80 ℃～90 ℃ hot water spirts, make the wherein Sweet fennel oil of a part of liquid state (its major ingredient is an alcohol), molten with partly borneol throw away together and leave away along with warm wash water, Sweet fennel oil is collected in oily water separation again, freezing it to five degrees below zero, borneol is that the overwhelming majority is separated out, and again centrifugal just collected borneol.This has just exempted existing the redistilled loaded down with trivial details work of oily brain, because the distilled oil brain must also have new part oil brain regeneration and come out, so turns over multiple distillation, and benefit is low, and equipment used and input manpower are all much more than the method for hot water wash oil.

Though improvement and not obvious and great also is very economical like this.

Adopt novel method of the present invention to substitute after the traditional technology, just can make the yield of thick borneol reach 55～62% safely and efficiently, certainly, this is concerning the terebinthine input amount of high-quality.Yield rate in thick borneol is 62.5%, and total recovery can reach 34%～39%, approximately only needs three tons of high-quality turps just can produce one ton of borneol, per ton can be less with about half ton turps.Add half ton of unslaked lime, the consumption that makes 30% white liquor reduces to 100 kilograms of less thaies from original 1.8 tons.Adding 1.5 tons of industrial sulphuric acids makes oxalic acid consumption reduce about 70%.Because the vitriolic of unslaked lime and 92% is cheap, estimate that therefore resulting cost can reduce about 20%.

Bypass ins and outs and economic benefit, operation of the present invention is consistent with the current technology pattern: the starting material catalytic esterification obtains esterification mixture.Reaction oil behind the → removal sediment boils off white light oil → oxalic acid borneol acetate alkaline saponification, steams collection thick borneol → crystallization secondary and gets finished product.

Since have very big like this common point to exist, just should utilize this common point to greatest extent.From the angle of returns of investment and production management, the old scrap build of borneol factory is the implementing method of the best of the present invention on the contrary.

In order not influence the production of factory, transformation can be set about from alkaline hydrolysis saponification and oxalic acid recovery aspect earlier, promptly at first adopt: the big step of D2+D21+D22 → E2 → E21+D3 → E32 → E51, the little step that is aided with E33+E331 → E41 → E51 forms the partial circulating circle of a sulphuric acid soln and the systemic circulation circle of an oxalic acid.

The main flow of doing like this current technology is almost not influence, as long as can promptly implement, the investment of being reclaimed oxalic acid by caoxalate removes and can drop into then, outside regaining then, can also be benefited then.

Next is only uses boron titanium catalyst replacement B instead ₂O ₃Catalyzer or H ₂TiO ₃Catalyzer.Use H ₂TiO ₃The factory of catalyzer only needs in the making equipment of catalyzer if use the boron titanium catalyst instead, interpolates modulation Fe (BO ₂) ₃, the NaCl mixed solution additional reservoir just, its steams and takes off the enamel still that white light oil is exactly usefulness originally, what does not therefore need to make changes, be a simplest and the most direct Measures of technical the most convenient.Use B ₂O ₃The factory of catalyzer then should be provided with the making equipment of boron titanium catalyst comprehensively, and the container that white light oil is taken off in the steaming of irony is used instead enamel still, and volume also should enlarge three times, otherwise the requirement that does not just reach material balance.These bigger changes have bigger influence to the main flow on the production line, and disposable assault is finished after intending performing all preparation works earlier.

Make full use of the mild characteristic of boron titanium catalyst reaction, the volume of irony esterifying kettle is expanded to two cubic metres, making once feeds intake reaches the high levels of 800 kilograms of rectified oil of turpentines.This is a bold reform design, it also is the target that pursue, the isomery of camphor production also is the operation that very big danger is arranged, and Hua Liu company also appears the major disaster of isomery still blast, but from then on this can not draw and will use the technical conclusion that small vessels is avoided instead.Isomery can be with the large container more than three cubic metres, and the catalytic esterification of firpene oxalic acid uses bigger container also to be fine, as long as when using the boron titanium catalyst instead, relends and uses B ₂O ₃Catalytic all safety equipment and prior-warning device are taken precautions against, and just should adamantinely develop towards the direction of using large container.But this change involves the factory building height, and problems such as equipment translocation rearrangement are more when changing money, intends implementing at last before being arranged in old equipment scrapping.

Above-mentioned all argumentations are not to oppose to build Xin Chang in addition with technical scheme of the present invention, if old factory is long neglected and in disrepair, perhaps will move reconstruction, all adopt the present invention program reform that all facilities and production technique also call can not.All truly have the place of advantage in raw material, production and marketing, all adopt the present invention program to build Xin Chang in addition,, also belong to praiseworthy decision-making certainly in the hope of obtaining bigger net effect.

Reference: [1] Yu Jinquan etc., the research of solidifying acid catalysis α-Pai Xi esterification-saponification borneolum syntheticum

Chemistry of forest product and industry 1995 (1): 15～19[2] chief editor of Nanjing forest product industry institute university teaching material: the natural resin process technology,

P274 rises, borneolum syntheticum production.China Forest press publishes.

Claims (3)

1, a kind of firpene catalytic esterification---the method for saponification borneolum syntheticum, the characteristic of present method is: catalytic esterification is used composite boron-titanium based catalyst instead; Saponification is improved to interpolation calcium hydroxide, unites utilization with sodium hydroxide.

2, the method for esterifying and saponifying borneolum syntheticum according to claim 1 is characterized in that having used composite boron-titanium based catalyst: it is an industrial metatitanic acid through washing, adds alkali and washes, adds hydrochloric acid and washes, removes Na ₂SO ₄NaCl, and make PH between 4～5, filtering moisture content moves in the distilling kettle, and adding is given quantitative by 3 molecule NaBO before boiling ₂With 1 molecule FeCl ₃6H ₂The suspension liquid that the O proportioning is made fully mixes, and boiling is taken out morsel during to the dough shape and moved in the baking oven, progressively heats oven dry, at last it is crushed into powder; NaBO ₂Can be by H ₃BO ₃Synthetic with NaOH, and give quantitative H ₃BO ₃Usage quantity can only be within 1.5%～3% the scope of end product quality; Composite boron-titanium based catalyst has been inherited the manufacture craft of metatitanic acid catalyzer, has only increased and will mix Fe (BO ₂) ₃With the work of 3NaCl constituent, form thus it with boric anhydride catalyzer in the past in do not have the key distinction of no boron in titanium, the metatitanic acid catalyzer.

3, the method for esterifying and saponifying borneolum syntheticum according to claim 1 is characterized in that having used interpolation Ca (OH) ₂The improvement saponification process, within same reactor, its Ca (OH) ₂Application quantity, the NaOH that should meet per 2 molecular weight is with the Ca that adds a molecular weight (OH) ₂Condition.

Images