CN109824747A - Using the processing method and its application of the waste water that chromic anhydride production hydrocortisone is formed - Google Patents
Using the processing method and its application of the waste water that chromic anhydride production hydrocortisone is formed Download PDFInfo
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- hydrocortisone
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Abstract
Using the processing method and its application of the waste water that chromic anhydride production hydrocortisone is formed, it is related to hydrocortisone preparation technical field, the waste water formed using chromic anhydride production hydrocortisone is mixed with sodium hydrate aqueous solution, it is removed by filtration after insoluble matter after mixed solution heats up and excessive oxygen is added carries out oxidation reaction, after going moisture removal to be in thick to material the material evaporation of acquirement again, concentrated sulfuric acid aqueous solution is added and carries out acidification reaction, through filtering, obtain aqueous solution, it is dried again, obtains the mixture containing sodium sulphate and dichromic acid sodium salt.The present invention treated salt-mixture containing chromium can replace chromic anhydride progress re-oxidation reaction, alleviate the environmental protection pressure of current hydrocortisone enterprise production, the by-product sodium sulphate obtained after processing carries out bipolar film process and obtains sodium hydroxide and sulfuric acid solution, after being reprocessed, recycle the processing section of chromate waste water, overall process Matter Transfer utilizes, and reduces material waste.
Description
Technical field
The present invention relates to hydrocortisone preparation technical field, it is related specifically to the cycling and reutilization skill of wherein chromic anhydride used
Art.
Background technique
Hydrocortisone is a kind of glucocorticoid, is the maximum kind of yield in hormone medicine, hydrocortisone energy
Glycometabolism is influenced, has the effects that anti-inflammatory, antiviral, antiallergy.The substitution for being mainly used for adrenocortical insufficiency is controlled
Treat and congenital adrenal function hyperplasia disease treatment, it can also be used to rheumatoid arthritis, rheumatic fever, gout,
Bronchial asthma, anaphylactia, and can be used for severe infections and Hemorrhagic shock treatment etc..
Preparing hydrocortisone both at home and abroad all uses semisynthesis at present.It is obtained i.e. from natural products and contains above-mentioned steroid
The compound of body basic framework is raw material, then carries out structure of modification through chemical method and obtain.Select high-quality, sufficient, cheap day
Right based product is a great research topic of international pharmaceuticals industry always as steroid drugs synthesis material.Steroid drugs half
The starting material of synthesis is all the derivative of sterol.Diosgenin such as is obtained from yam family plant, sisal hemp soap is obtained from sisal hemp
Element obtains hecogenin from imperial tongue Zhu, obtains stigmasterol and cupreol from grease Litter, obtain from lanolin
Cholesterol.These all can serve as the semi-synthetic raw material of synthesizing steroid drug.Wherein Chinese yam saponin is widely used one kind
Raw material.When producing hydrocortisone using Chinese yam saponin, the process of chromic anhydride oxidation processes starting material is all utilized by one,
The step in, oxidation reaction that chromic anhydride carries out in dilute acetic acid solution occurs in the double bond of furan nucleus.Chromic anhydride is toxic, in oxygen
Contain a large amount of Cr in the industrial wastewater that chemical industry sequence generates6+And Cr3+, wherein C6+For extremely toxic substance, which is once ingested human body
Cancer can be caused by inside reaching certain amount, once have many researchers and producers to wish to substitute chromic anhydride with other oxidants,
These methods are also all in verifying.In industrial practice, using most still chromic anhydrides.
Summary of the invention
First item of the invention is to propose a kind of wastewater treatment method formed using chromic anhydride production hydrocortisone.
The present invention the following steps are included:
1) waste water formed using chromic anhydride production hydrocortisone is mixed with sodium hydrate aqueous solution, after being removed by filtration insoluble matter
Mixed solution is warming up to 50~95 DEG C, oxygen is then added and carries out oxidation reaction, until after dark brown brown is presented in mixed solution
Continue oxygen 0.5~2 hour again;
The chromium contained in the waste water for using chromic anhydride production hydrocortisone to be formed is most of with Cr3+Form exists, and there is also not anti-
The Cr answered6+.PH value is adjusted using sodium hydroxide in step 1) of the present invention, makes unreacted Cr6+Generate Na2CrO4, and make Cr3+?
In alkaline solution, with air oxidation at CrO4 2-.The present invention is passed through excessive air, it is ensured that Cr3+It is oxidized life under alkaline condition
At Cr6+, in case subsequent further reaction.
The relevant reaction equation of step 1) are as follows:
Cr3++3OH-=Cr(OH)3=H2O +HCrO2=H++CrO2 -+ H2O
2CrO2 -+O2+4OH-=2 CrO4 2-+2 H2O
H2Cr2O7+2NaOH=Na2Cr2O7+2 H2O
The above H2Cr2O7For unreacted dichromic acid.
2) material that step 1) obtains is evaporated moisture removal to material in after thick, concentrated sulfuric acid aqueous solution is added
Acidification reaction is carried out, is filtered after reaction, sulfate crystal object and aqueous solution is obtained respectively, aqueous solution is done
It is dry, obtain the mixture containing sodium sulphate and dichromic acid sodium salt.
Generate the reaction equation of sodium sulphate and sodium dichromate salt-mixture:
2Na2CrO4+ H2SO4=Na2Cr2O7 +Na2SO4+H2O
Generate the reaction equation of sodium sulphate:
H2SO4+ 2NaOH=Na2SO4+ 2H2O
The present invention is acidified using sulfuric acid, makes CrO4 2-It is fully converted into CrO7 2-, obtain the Na for being mixed with sodium sulphate2Cr2O7It is molten
Liquid contains Na after drying2Cr2O7Salt-mixture chromic anhydride can be replaced to be back to use the oxidation section of hydrocortisone.It generates simultaneously
Sulfate crystal can be electrolysed by Bipolar Membrane, sodium hydroxide and sulfuric acid is prepared, these Matter Transfers are spare.
The present invention realizes the processing of chromate waste water in hydrocortisone production, and overall process step is simple, and treated
Salt-mixture containing chromium can replace chromic anhydride and carry out re-oxidation reaction, alleviate the environmental protection pressure of current hydrocortisone enterprise production
Power, the by-product sodium sulphate obtained after processing carry out bipolar film process and obtain sodium hydroxide and sulfuric acid solution, after being reprocessed, follows
Ring uses the processing section of chromate waste water, and overall process Matter Transfer utilizes, and reduces material waste.
Further, in step 1) of the present invention, the waste water mixed with sodium hydrate aqueous solution to pH be 7.8~
8.5, then it is filtered again.Using ensure reaction system as under alkaline condition, Cr3+It can be by O2It is oxidized to Cr6+, suitable pH value
System is set to obtain transition state CrO2-。
In the step 1), the mode that oxygen is added is to be passed through clean air.It is used in the present invention and passes through clean sky
The method substitution oxygen of gas is conducive to save production cost.
In the step 1), oxygen is added after the mixed solution is warming up to 75~85 DEG C.Cr3+Become using air oxidation
At Cr6+Need certain temperature.Suitable temperature makes Cr3+It is able to maximum be converted into Cr6+。
In the step 2, the pH value of system is 6.8~7.5 when the acidification reaction, can make Na2CrO4It is fully anti-
Na should be generated2Cr2O7.If pH value is too low, acidification rate is excessively high, and a large amount of free acids are present in system, is not suitable for and reacts.If
PH value is higher, then acidification rate is too low, and sodium chromate cannot be fully converted to sodium dichromate.
The progress for the benefit of reacted, in the step 2, the concentration of the concentrated sulfuric acid aqueous solution is 60~70%(wt).Add
Enter concentrated sulfuric acid solution, so that sodium chromate is more rapidly performed by acidification into sodium dichromate, react very exothermic, system is not added
Heat can be prepared by sodium dichromate.
It is 75~85 DEG C that the temperature to heat up after sodium hydroxide is added in step 1), it can be ensured that the generation of oxidation reaction.
Second item of the invention is propose that above processing method obtains mixed containing sodium sulphate and dichromic acid sodium salt
Close the application of object.
The mixture replacing chromic anhydride containing sodium sulphate and dichromic acid sodium salt that above-mentioned processing method is obtained carries out hydrogenation can
Pine in oxidation reaction.This method is effectively utilized waste, has saved production cost, while nor affecting on reactor product receipts
Rate and purity.
Further, the mixture containing sodium sulphate and dichromic acid sodium salt is adjusted to pH value with the concentrated sulfuric acid as 2~3
Carry out the oxidation reaction of hydrocortisone.When being reacted using the salt-mixture substitution chromic anhydride generated after processing waste water containing chrome, need
It keeps in acid condition, oxidation reaction can just occur.
Specific method is: first by the mixture containing sodium sulphate and dichromic acid sodium salt, sodium acetate, deionized water and dense
Aqueous sulfuric acid is mixed to pH value to 2~3, obtains chromic acid solution;In a kettle by Chinese yam saponin, aceticanhydride and first part of glacial acetic acid
It vacuumizes after mixing, then heats up, be 200 DEG C, pressure 5kg/cm in temperature2Reaction is cooling after under conditions above, then
Second part of glacial acetic acid is added, after being cooled to 5~7 DEG C, adds the chromic acid solution, oxidation is kept the temperature under the conditions of 60~70 DEG C
When being warming up to 95 DEG C after reaction extremely to carry out after distilling out acetic acid, then being warming up to 110 DEG C or more, uses vacuum distillation apparatus instead and return
Receive acetic acid, then through cooling, be diluted with water, be filtered, washed, obtain diene alcohol ketone crude product.
Above-mentioned Chinese yam saponin, aceticanhydride, first part of glacial acetic acid, sodium acetate, second part of glacial acetic acid, it is described containing sodium sulphate and again
The mixture of chromic acid sodium salt and the feed weight ratio of water are 1: 1.5: 0.5: 0.25: 2: 0.5: 0.8.I.e. salt-mixture substitutes chromic anhydride
Additional amount is to carry out addition with the molar ratio 1: 1 of chromium in chromic anhydride according to salt-mixture to react.
Detailed description of the invention
Attached drawing 1 is hydrocortisone chromic anhydride cycling and reutilization flow chart.
Specific embodiment
One, the treatment process of the waste water of workshop section is washed after chromic anhydride oxidation:
Embodiment 1
1, the waste water 8L that workshop section is washed after taking chromic anhydride to aoxidize is added in reactor, then sodium hydroxide is added to the reactor, will mix
The pH value of zoarium system is adjusted to 7.8, is removed by filtration insoluble matter by filter, is then warming up to 85 DEG C, blasts clean air,
Dark brown brown is presented to solution, and persistently blasts air 1 hour.
2, sulfuric acid oxidation:
Moisture is removed into the heating evaporation of above-mentioned reactor, when material is in thick, it is 70% that concentration is slowly added dropwise into above-mentioned solution
(wt) aqueous sulfuric acid, until the pH value of the mixed system reaches 6.8, it is reacted to make CrO in solution4 2-It is fully converted into
Cr2O7 2-, and form sodium sulfate salt crystallization.
Then it is removed by filtration the crystallization of sodium sulphate, remaining solution is dried to get sodium sulphate and dichromic acid is contained
The mixture of sodium.
Product is respectively as follows: sulfate crystal 285g, the sodium dichromate mixture 580g containing micro sodium sulphate.
Embodiment 2
1, workshop section's waste water 10L is washed after taking chromic anhydride to aoxidize, and sodium hydroxide is added, is tuned into pH value to 8.5, crosses and filter out by filter
Fall insoluble matter, be then warming up to 75 DEG C, blast clean air, until dark brown brown is presented in solution, and it is small persistently to blast air 1.5
When.
3, sulfuric acid acidification dehydration:
Moisture is removed into the heating evaporation of above-mentioned reactor, when material is in thick, it is 60% that concentration is slowly added dropwise into above-mentioned solution
(wt) aqueous sulfuric acid, adjusts pH 7, reacted to make CrO in solution4 2-It is fully converted into Cr2O7 2-, and form sodium sulfate salt
Crystallization.
Be removed by filtration the crystallization of sodium sulphate, by obtained aqueous solution it is dry after, obtain containing sodium sulphate and sodium dichromate
Mixture.
Product is respectively as follows: sulfate crystal 350g, the sodium dichromate mixture 730g containing micro sodium sulphate.
Two, the utilization of sodium sulfate salt crystallization:
The sodium sulfate salt obtained above is crystallized and carries out Bipolar Membrane electrolysis, obtains sodium hydroxide and dilution heat of sulfuric acid, sodium hydroxide
It is spare that solution is dried to obtain solid, and dilution heat of sulfuric acid carries out being concentrated into 80% spare.
Relevant reaction equation are as follows:
2Na2SO4+ 6H2O=4NaOH+2H2SO4+ 2H2↑+O2↑+H2O 。
Using three compartment Bipolar Membrane methods, electrolytic cell assembly size 400mm*800mm, the effective membrane area of film group device is 15m2,
Anode chamber generates sulfuric acid and oxygen, and cathode chamber generates sodium hydroxide and hydrogen,.
Three, the application of the mixture containing sodium sulphate and sodium dichromate:
1, application examples 1: the salt-mixture substitution chromic anhydride obtained using embodiment 1 carries out the oxidation reaction in hydrocortisone.
It weighs respectively: 1000 g of Chinese yam saponin, 1500 g of aceticanhydride, first part of glacial acetic acid: 500 g, 250 g of sodium acetate,
Two parts of glacial acetic acid: 800 g of 500 g of salt-mixture and water that 2000 g, embodiment 1 obtain.
Salt-mixture, sodium acetate and the deionized water mixing that weighed embodiment 1 is obtained, and it is 70%(wt that concentration, which is added)
Aqueous sulfuric acid, adjust the pH value of mixed system to 2~3, be prepared into chromic acid solution, it is spare.
By in Chinese yam saponin, aceticanhydride and first part of glacial acetic acid investment reaction kettle, first vacuumize, then heating makes in reaction kettle
Temperature reach 200 DEG C, pressure 5kg/cm2More than, react half an hour.After reaction, cooling, second part of glacial acetic acid is added,
5~7 DEG C are cooled back to, the above chromic acid solution is added, it is then made to be warming up to 60~70 DEG C, insulation reaction 20 minutes naturally.
After oxidation reaction, heat to 95 DEG C, start be distilled to recover acetic acid, temperature be gradually raised to 110 DEG C with
When upper, vacuum distillation apparatus recovery of acetic acid was used instead to certain volume, cools down, be diluted with water, be filtered, washed, obtain diene alcohol ketone
Crude product.
Product yield, product purity are shown in Table 1.
2, application examples 2: the oxidation reaction in hydrocortisone is carried out using the substitution chromic anhydride of salt-mixture made from embodiment 2.
Specific reaction step and method are the same as application examples 1.Product yield, product purity are shown in Table 1.
3, oxidation reaction comparative example: is carried out using chromic anhydride.
It weighs respectively: 1000 g of Chinese yam saponin, 1500 g of aceticanhydride, first part of glacial acetic acid: 500 g, 250 g of sodium acetate,
Two parts of glacial acetic acid: 800 g of 2000 g, 380 g of chromic anhydride and water.
Chromic anhydride, sodium acetate and deionized water are prepared by mixing into chromic anhydride solution, it is spare.
By in Chinese yam saponin, acetic anhydride and first part of glacial acetic acid investment reaction kettle, first vacuumize, then heating makes reaction kettle
Interior temperature reaches 200 DEG C, pressure 5kg/cm2More than, react half an hour.After reaction, cooling, second portion of ice vinegar is added
Acid is cooled back to 5~7 DEG C, and the chromic anhydride solution prepared in advance is added, so that it is warming up to 60~70 DEG C naturally, insulation reaction
20 minutes.After oxidation reaction, 95 DEG C are heated to, starts to be distilled to recover acetic acid, temperature is gradually raised to 110 DEG C or more
When, vacuum distillation apparatus recovery of acetic acid is used instead to certain volume, is cooled down, is diluted with water, is filtered, washed, it is thick to obtain diene alcohol ketone
Product.
Product yield and purity are shown in Table 1.
The conventional chromic anhydride reaction of table 1 and chromic anhydride recycle the product yield and purity table of reaction
Number | Diene alcohol ketone yield/% | Diene alcohol ketone purity/% |
1 product of application examples | 56 | 95 |
2 product of application examples | 54 | 96 |
Comparative example product | 55 | 96 |
Seen from table 1, the mixture replacing chromium containing sodium sulphate and dichromic acid sodium salt that the present invention is used to obtain after at waste water
Acid anhydride carry out hydrocortisone in oxidation reaction, be not only effectively utilized waste, at the same nor affect on reactor product yield and
Purity.
Claims (10)
1. using the processing method for the waste water that chromic anhydride production hydrocortisone is formed, comprising the following steps:
1) waste water formed using chromic anhydride production hydrocortisone is mixed with sodium hydrate aqueous solution, after being removed by filtration insoluble matter
Mixed solution is warming up to 50~95 DEG C, excessive oxygen is then added and carries out oxidation reaction, until mixed solution presentation is dark brown brown
Continue oxygen 0.5~2 hour again after color;
2) after going moisture removal to be in thick to material the material evaporation that step 1) obtains, concentrated sulfuric acid aqueous solution is added and is acidified
Reaction, is filtered after reaction, obtains sulfate crystal object and aqueous solution respectively, aqueous solution is dried, must be contained
The mixture of sodium sulphate and dichromic acid sodium salt.
2. the processing method of the waste water formed according to claim 1 using chromic anhydride production hydrocortisone, it is characterised in that:
In the step 1), it is 7.8~8.5 that the waste water, which is mixed with sodium hydrate aqueous solution to pH, is then filtered again.
3. the processing method of the waste water formed according to claim 1 using chromic anhydride production hydrocortisone, it is characterised in that:
In the step 1), the mode that oxygen is added is to be passed through clean air.
4. the processing method of the waste water formed according to claim 1 using chromic anhydride production hydrocortisone, it is characterised in that:
In the step 1), oxygen is added after the mixed solution is warming up to 75~85 DEG C.
5. the processing method of the waste water formed according to claim 1 using chromic anhydride production hydrocortisone, it is characterised in that:
In the step 2, the pH value of system is 6.8~7.5 when the acidification reaction.
6. the processing method of the waste water formed according to claim 1 using chromic anhydride production hydrocortisone, it is characterised in that:
In the step 2, the concentration of the concentrated sulfuric acid aqueous solution is 60~70%(wt).
7. the application for the mixture containing sodium sulphate and dichromic acid sodium salt that processing method as described in claim 1 obtains, special
Sign is: the mixture replacing chromic anhydride containing sodium sulphate and dichromic acid sodium salt that above-mentioned processing method is obtained carry out hydrogenation can
The oxidation reaction of pine.
8. application according to claim 7, it is characterised in that: by the mixture containing sodium sulphate and dichromic acid sodium salt
Being adjusted to pH value with the concentrated sulfuric acid is 2~3 oxidation reactions for carrying out hydrocortisone.
9. application according to claim 8, it is characterised in that: the first mixing by described containing sodium sulphate and dichromic acid sodium salt
Object, sodium acetate, deionized water and concentrated sulfuric acid aqueous solution are mixed to pH value to 2~3, obtain chromic acid solution;In a kettle by Chinese yam
It vacuumizes after saponin, aceticanhydride and first part of glacial acetic acid mixing, then heats up, be 200 DEG C, pressure 5kg/cm in temperature2The above item
Reaction is cooling after under part, adds second part of glacial acetic acid, after being cooled to 5~7 DEG C, adds the chromic acid solution,
Kept the temperature under the conditions of 60~70 DEG C oxidation reaction be warming up to after 95 DEG C carry out distilling out acetic acid after, then be warming up to 110 DEG C
When above, use vacuum distillation apparatus recovery of acetic acid instead, then through cooling, be diluted with water, be filtered, washed, obtain diene alcohol ketone crude product.
10. application according to claim 9, it is characterised in that: the Chinese yam saponin, aceticanhydride, first part of glacial acetic acid, acetic acid
Sodium, second part of glacial acetic acid, the mixture containing sodium sulphate and dichromic acid sodium salt and water feed weight ratio be 1: 1.5: 0.5
∶0.25∶2∶0.5∶0.8。
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Cited By (1)
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CN111560524A (en) * | 2020-06-15 | 2020-08-21 | 中国科学院过程工程研究所 | Method for inhibiting reduction of sodium chromate in circulating liquid in vanadium slag vanadium-chromium co-extraction process |
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CN103044513A (en) * | 2012-12-20 | 2013-04-17 | 湖北省丹江口开泰激素有限责任公司 | Method for manufacturing dehydropregnenolone acetate by using mixed solvent |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN111560524A (en) * | 2020-06-15 | 2020-08-21 | 中国科学院过程工程研究所 | Method for inhibiting reduction of sodium chromate in circulating liquid in vanadium slag vanadium-chromium co-extraction process |
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