CN109796304A - A kind of synthetic method of BED - Google Patents
A kind of synthetic method of BED Download PDFInfo
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- CN109796304A CN109796304A CN201910131466.8A CN201910131466A CN109796304A CN 109796304 A CN109796304 A CN 109796304A CN 201910131466 A CN201910131466 A CN 201910131466A CN 109796304 A CN109796304 A CN 109796304A
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- 238000010189 synthetic method Methods 0.000 title claims abstract description 21
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 81
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 16
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 16
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 238000000746 purification Methods 0.000 claims abstract description 11
- 239000012043 crude product Substances 0.000 claims abstract description 8
- BBGINXZYXBFSEW-UHFFFAOYSA-N [Cu].C#C Chemical compound [Cu].C#C BBGINXZYXBFSEW-UHFFFAOYSA-N 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 48
- 239000007788 liquid Substances 0.000 claims description 45
- 239000007791 liquid phase Substances 0.000 claims description 26
- 239000007789 gas Substances 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000009833 condensation Methods 0.000 claims description 11
- 230000005494 condensation Effects 0.000 claims description 11
- 238000005201 scrubbing Methods 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 7
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 7
- 239000004571 lime Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000008234 soft water Substances 0.000 claims description 7
- 238000007664 blowing Methods 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000012808 vapor phase Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 3
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 230000005587 bubbling Effects 0.000 claims description 2
- 230000006835 compression Effects 0.000 claims description 2
- 238000007906 compression Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 3
- 238000005984 hydrogenation reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical class OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- LXNHXLLTXMVWPM-UHFFFAOYSA-N pyridoxine Chemical compound CC1=NC=C(CO)C(CO)=C1O LXNHXLLTXMVWPM-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- MJBPUQUGJNAPAZ-UHFFFAOYSA-N Butine Natural products O1C2=CC(O)=CC=C2C(=O)CC1C1=CC=C(O)C(O)=C1 MJBPUQUGJNAPAZ-UHFFFAOYSA-N 0.000 description 1
- 206010020852 Hypertonia Diseases 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- RADKZDMFGJYCBB-UHFFFAOYSA-N pyridoxal hydrochloride Natural products CC1=NC=C(CO)C(C=O)=C1O RADKZDMFGJYCBB-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 239000011726 vitamin B6 Substances 0.000 description 1
- 235000019158 vitamin B6 Nutrition 0.000 description 1
- 229940011671 vitamin b6 Drugs 0.000 description 1
Abstract
A kind of synthetic method of BED, has follow steps: 1) BYD is synthesized, using formaldehyde and acetylene as raw material, for acetylene copper as catalyst, synthesis obtains BYD, 2) BYD removes color, utilize active carbon purifying BYD, obtain purification BYD, 3) synthesis BED, BED crude product is prepared using hydrogenation method, 4) it is dehydrated, moisture in removing BED crude product, 5) rectifying, further purification obtains BED fine work.The processing step of synthetic method of the present invention is simple, mild condition, and synthesis cost is lower, and the BED purity is high synthesized can effectively meet the needs of downstream client.
Description
Technical field
The present invention relates to chemical field, in particular to a kind of synthetic method of BED.
Background technique
BED is the abbreviation of Isosorbide-5-Nitrae-butylene glycol, colourless or light yellow liquid, no mechanical admixture, soluble easily in water, ethyl alcohol, third
Ketone is practically insoluble in lower aliphatic hydrocarbon or aromatic hydrocarbons.Energy participates in the reactions such as esterification, alkylation, cyclisation, substitution, addition and isomerization.
It is mainly used for producing the intermediate of insecticide, agricultural chemicals and vitamin B6, is used for polymer production on a small quantity.
Currently, BED is prepared mainly with Isosorbide-5-Nitrae-butynediols (BYD) for raw material through catalytic hydrogenation, with a small amount of 1,
4 butylene glycols, which further react, generates 1,4 butanediols.
The BED being prepared in this way usually contains a small amount of Isosorbide-5-Nitrae butanediol, and product quality is caused to decline.This
Outside, directly using Isosorbide-5-Nitrae-butynediols as raw material, also with the defect of higher cost.Therefore, how to prepare at lower cost
High-quality BED is those skilled in the art's urgent problem to be solved.
Summary of the invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide the synthetic method of BED a kind of, processing step letters
Single, mild condition, synthesis cost is lower, and the BED purity is high synthesized can effectively meet the needs of downstream client.
The technical scheme is that a kind of synthetic method of BED, has follow steps,
1) BYD is synthesized
Using formaldehyde as liquid phase, acetylene gas is bubbled dispersion in the liquid phase, and acetylene copper is as catalyst, reaction temperature 93
DEG C, reaction pressure 156Kpa, synthesis obtains Isosorbide-5-Nitrae-butyne diol solutions (BYD), after filtering, spare into BYD collecting tank；
2) BYD removes color
1. active carbon is immersed in soft water, adsorption liquid is obtained, the BYD solution of step 1) synthesis is put into reaction kettle,
It vacuumizes, adsorption liquid is added, remove color；
2. under stirring, being warming up to 75 DEG C, 1h is kept the temperature；
3. being centrifuged, extracting centrifugal liquid；
3) BED is synthesized
1. catalyst liquid is obtained by catalyst soak in soft water, in the centrifugate investment reaction kettle that step 2) is obtained,
It vacuumizes, catalyst liquid is added, until vacuum degree is -0.04MPa；
2. being filled with nitrogen into reaction kettle to 0.1MPa, then it is evacuated to -0.04MPa, nitrogen is filled with into reaction kettle extremely
0.1MPa, then it is evacuated to -0.06MPa, persistently vacuumize 2-3min；
3. being filled with hydrogen into reaction kettle to 0.5MPa, stirring is warming up to 85 DEG C, and control reaction temperature is 110 ± 5 DEG C,
To BYD content less than 0.5%, reaction terminates, centrifugation, extracting centrifugal liquid；
4) it is dehydrated
In the centrifugate investment dehydrating kettle that step 3) is obtained, vacuumizing, stirring heating, until anhydrous ooze, dehydration is finished,
Blowing obtains crude product BED；
5) rectifying
In the crude product BED investment distillation still that step 4) is obtained, -0.09MPa is evacuated to hereinafter, control vapo(u)rizing temperature is
170 DEG C, until there is distillate, distillation is finished, and blowing obtains purification BED.
Further, the step 1) formaldehyde enters BYD reactor liquid phase, and acetylene gas, which is bubbled, enters BYD reactor bottom
Part dissipates in the liquid phase.
Further, the unreacting gas of the BYD reactor head discharge enters scrubbing tower, after washed, makees through compression
It is dispersed in step 1) liquid phase for acetylene gas bubbling, the washing is formaldehyde with liquid, and the washing extracted out from wash tower bottoms is used
Liquid part is used as step 1) liquid phase after cooling, and remaining part returns to scrubbing tower as washing liquid, forms circulation, the BYD
Sodium carbonate is added in reactor as buffer.
Further, it filters described in step 1), is filtered using candle filter, it is spare into BYD collecting tank.
Further, after BYD solution in BYD collecting tank is preheated, formaldehyde recycle column, the formaldehyde recycle column are pumped to
The Vapor phase partial at top is used as step 1) liquid phase through condensation, and remaining part enters condensation by contact tower after cooling, forms lime set, coagulates
Liquid is divided into four parts, and first part is back to formaldehyde circulation tower top, after exchanging heat with the BYD solution being pumped in formaldehyde recycle column,
Obtain purification BYD, second part is used as step 1) liquid phase, Part III after cooling, return condensation by contact tower as spray liquid,
Part IV returns to scrubbing tower as washing liquid.
Preferably, catalyst described in step 3) is Raney's nickel.
Further, the step 4) dehydrating kettle is opened matched vacuum system and vacuumized, heated up using steam, until temperature
Degree rises to 95 DEG C, and dehydrating kettle vacuum degree is -0.08MPa, is warming up to 125 DEG C, closes vacuum system.
It has the advantages that by adopting the above technical scheme
1, synthetic method of the present invention synthesizes BED using formaldehyde, acetylene as raw material, can effectively reduce the synthesis of BED at
This.
2, synthetic method of the present invention, using acetylene copper as catalyst, controlling reaction temperature is 93 DEG C, and reaction pressure is
156Kpa, it is few that synthesis obtains Isosorbide-5-Nitrae-butyne diol solutions (BYD) high income, by-product, can effectively improve the utilization efficiency of raw material.If
Temperature is lower than 156Kpa lower than 93 DEG C, reaction pressure, and reaction rate is slow, reaction efficiency is lower, is unfavorable for BYD synthesis, if temperature
Be higher than 156Kpa higher than 93 DEG C, reaction pressure, the more high boiling impurity of by-product, and the high requirements on the equipment, cause production cost compared with
Height, and be unfavorable for keeping the safety in production.
3, synthetic method of the present invention, obtained BYD are decolourized, after purification, as raw material for synthesizing BED, improve BED's
Quality.
4, synthetic method of the present invention sets gas using nitrogen when synthesizing BED using BYD repeatedly, lacks reaction kettle inner height
Oxygen guarantees that reaction is normally gone on smoothly.It is 110 ± 5 DEG C, pressure 0.5Mpa by control reaction temperature, so that synthesis obtains
BED high income, by-product, especially Isosorbide-5-Nitrae butanediol is few, can effectively improve the quality of BED.If reaction temperature is lower than 105 DEG C, pressure
Power is too low, and reaction rate is slow, reaction efficiency is lower, be unfavorable for BED synthesis, if reaction temperature be higher than 115 DEG C, hypertonia, then
It is more to will lead to by-product, and the high requirements on the equipment, cause production cost higher, and is unfavorable for keeping the safety in production.
5, sodium carbonate is added in BYD reactor as buffer, for neutralizing by-product in liquid phase for synthetic method of the present invention
Formic acid improves the quality of BYD.
6, synthetic method of the present invention is pumped to formaldehyde recycle column, the first after BYD solution in BYD collecting tank is preheated
Vapor phase partial at the top of aldehyde recycle column is used as step 1) liquid phase through condensation, and remaining part enters condensation by contact tower after cooling, shape
At lime set, the formaldehyde being mingled in BYD solution, methanol are efficiently separated, while improving formaldehyde utilization efficiency, also effectively improves BYD
Purity.Lime set is divided into four parts, and first part is back to formaldehyde circulation tower top, molten with the BYD that is pumped in formaldehyde recycle column
After liquid heat exchange, purification BYD is obtained as the raw material of synthesis BED and further increases the synthesis quality of BED.Second part is as step
Rapid 1) liquid phase, Part III after cooling, return to condensation by contact tower as spray liquid, Part IV returns to scrubbing tower as washing
With liquid, so that each processing step is formed Efficient Cycle, meet enterprise practical demand.
Through applicant's pilot production, the product synthesized using synthetic method of the present invention, target product Isosorbide-5-Nitrae-butylene two
Alcohol (BED) content >=96%, Isosorbide-5-Nitrae butanediol content≤1.0%, moisture content≤1.5%, butynediols content≤0.5%.
It is further described combined with specific embodiments below.
Specific embodiment
Not specified concrete operations technique in embodiment, condition usually according to normal condition or according to the manufacturer's recommendations into
Row, does not indicate the equipment or industrial chemicals of concrete model, usually equipment conventional in chemical field or raw material.
Embodiment 1
1) BYD is synthesized
Acetylene gas enters acetylene recycle compressor through acetylene resistance Xie Ta, and the gas-liquid mixture compressed enters entrance and washes
Wash tower bottom after gas-liquid separation, bottom liquid after the cold matched cooler of entrance scrubbing tower is cooling, a part be recycled into
For mouth circulation column overhead as spray liquid, remainder returns to acetylene recycle compressor after cooling, and entrance washs the second of column overhead
Alkynes gas enters BYD reactor.
Enter BYD reactor as liquid phase using formaldehyde and circulation formaldehyde, acetylene gas, which is bubbled, enters BYD reactor bottom
In the liquid phase, for acetylene copper as catalyst, reaction temperature is 93 DEG C, reaction pressure 156Kpa for dispersion, synthesizes BYD.BYD reaction
The unreacting gas (including acetylene, water, formaldehyde and inert gas) of device discharge, into wash tower bottoms, scrubbing tower top, middle part spray
What is entered is washed through cooling washing with liquid and unreacting gas counter current contacting, and water, formaldehyde, the methanol in unreacting gas are removed, and
Reaction heat is removed, washing lotion uses formaldehyde with liquid.The unreacting gas (being rich in acetylene) of column overhead is washed, the overwhelming majority returns to acetylene and follows
Ring compressor, remainder enter tail gas washing tower it is washed after, drain into acetylene torch.The washing extracted out from wash tower bottoms is used
Liquid returns to BYD reactor as liquid phase after cooling, and remainder returns to scrubbing tower as washing liquid, forms circulation.This reality
It applies in example, in order to neutralize the formic acid in BYD reactor liquid phase, suitable sodium carbonate is added as buffer.
The liquid phase of end of reaction is filtered through candle filter in BYD reactor, into BYD collecting tank, in BYD collecting tank
BYD liquid pumps out after secondary filtration, is pumped into thick BYD tank, and the discharge gas at the top of BYD collecting tank is solidifying with steam through tail gas washing tower
Liquid washs heel row to acetylene torch.
After filtering, preheating is pumped to formaldehyde recycle column to thick BYD in thick BYD tank, for by the formaldehyde in thick BYD, first
Alcohol is isolated.Formaldehyde recycles the Vapor phase partial of column overhead after condensing, and forms circulation formaldehyde, into BYD reactor as liquid phase,
Remaining part enters condensation by contact tower after cooling, forms lime set, and lime set is divided into four parts, and first part is back to formaldehyde circulation
Column overhead after recycling heat with the thick BYD heat exchange being pumped in formaldehyde recycle column, obtains purification BYD through cooling, into smart BYD
Tank, second part after cooling, return to condensation by contact tower as spray liquid, Part IV as step 1) liquid phase, Part III
Scrubbing tower is returned as washing liquid.
2) BYD removes color
1. specially in the plastic barrel of 200L volume, injecting 120Kg soft water in open-top receptacle, 2Kg active carbon being immersed in
In soft water, adsorption liquid is obtained.By in the purification BYD investment reaction kettle of step 1) synthesis, amounts to 1200 tons, vacuumize, be added and inhale
Attached liquid removes color；
2. under stirring, being warming up to 75 DEG C, 1h is kept the temperature；
3. it is centrifuged, specifically, using scraper type self-discharging centrifugal machine, extracting centrifugal liquid；
3) BED is synthesized
1. specially 2Kg Raney's nickel is completely soaked by the plastic barrel of 200L volume, injection 100Kg soft water in open-top receptacle
In entering, catalyst liquid is obtained.The centrifugate that step 2) is obtained amounts to 900kg, puts into reaction kettle, vacuumizes, and catalysis is added
Agent liquid, until vacuum degree is -0.04MPa；
2. being filled with nitrogen into reaction kettle to 0.1MPa, then it is evacuated to -0.04MPa, nitrogen is filled with into reaction kettle extremely
0.1MPa, then it is evacuated to -0.06MPa, persistently vacuumize 2-3min；
3. being filled with hydrogen into reaction kettle to 0.5MPa, reaction kettle stirring is opened, 85 DEG C is warming up to using steam, closes and steam
Vapour, reaction kettle enters normergic state at this time, the use of circulation water management reaction temperature is 110 ± 5 DEG C.Reaction kettle reacts at this time
Pressure can be declined with reaction temperature, be typically reduced between 0.35-0.48Mpa.After sustained response 1-3h, sampling analysis,
To BYD content less than 0.5%, reaction terminates, centrifugation, extracting centrifugal liquid.Through analyzing, each component content is as follows in centrifugate:
H2O: it does not analyze
BDO :≤1.0%
BED: >=96.0%
BYD :≤0.5%.
4) it is dehydrated
In the centrifugate investment dehydrating kettle that step 3) is obtained, opens matched vacuum system and vacuumize, utilize steam liter
Temperature, until temperature rises to 95 DEG C, dehydrating kettle vacuum degree is -0.08MPa, is warming up to 125 DEG C, closes vacuum system, until anhydrous ooze,
Dehydration finishes, and blowing obtains crude product BED.
5) rectifying
In the crude product BED investment distillation still that step 4) is obtained, -0.09MPa is evacuated to hereinafter, control vapo(u)rizing temperature is
170 DEG C, until there is distillate, distillation is finished, and blowing obtains purification BED.It is as follows to refine each component content in BED for sampled analysis:
Isosorbide-5-Nitrae-butylene glycol (BED) content >=96%, Isosorbide-5-Nitrae butanediol content≤1.0%, moisture content≤1.5%, butine
Glycol content≤0.5%.
Claims (7)
1. a kind of synthetic method of BED, which is characterized in that it has follow steps,
1) BYD is synthesized
Using formaldehyde as liquid phase, acetylene gas is bubbled dispersion in the liquid phase, and for acetylene copper as catalyst, reaction temperature is 93 DEG C,
Reaction pressure is 156Kpa, and synthesis obtains Isosorbide-5-Nitrae-butyne diol solutions (BYD), after filtering, spare into BYD collecting tank；
2) BYD removes color
1. active carbon is immersed in soft water, adsorption liquid is obtained, by the BYD solution investment reaction kettle of step 1) synthesis, is taken out true
Adsorption liquid is added in sky, removes color；
2. under stirring, being warming up to 75 DEG C, 1h is kept the temperature；
3. being centrifuged, extracting centrifugal liquid；
3) BED is synthesized
1. obtaining catalyst liquid by catalyst soak in soft water, in the centrifugate investment reaction kettle that step 2) is obtained, take out true
Catalyst liquid is added in sky, until vacuum degree is -0.04MPa；
2. being filled with nitrogen into reaction kettle to 0.1MPa, then it is evacuated to -0.04MPa, nitrogen is filled with into reaction kettle extremely
0.1MPa, then it is evacuated to -0.06MPa, persistently vacuumize 2-3min；
3. being filled with hydrogen into reaction kettle to 0.5MPa, stirring is warming up to 85 DEG C, and control reaction temperature is 110 ± 5 DEG C, until BYD
Less than 0.5%, reaction terminates content, centrifugation, extracting centrifugal liquid；
4) it is dehydrated
In the centrifugate investment dehydrating kettle that step 3) is obtained, vacuumize, stirring heating, until anhydrous ooze, dehydration is finished, blowing
Obtain crude product BED；
5) rectifying
In the crude product BED investment distillation still that step 4) is obtained, -0.09MPa is evacuated to hereinafter, control vapo(u)rizing temperature is 170
DEG C, until there is distillate, distillation is finished, and blowing obtains purification BED.
2. the synthetic method of BED according to claim 1, which is characterized in that the step 1) formaldehyde enters BYD reactor
Liquid phase, acetylene gas, which is bubbled, enters the dispersion of BYD reactor bottom in the liquid phase.
3. the synthetic method of BED according to claim 2, which is characterized in that the BYD reactor head is discharged not anti-
Should gas enter scrubbing tower, after washed, through compression as acetylene gas bubbling be dispersed in step 1) liquid phase, liquid is used in the washing
For formaldehyde, the washing extracted out from wash tower bottoms uses liquid part after cooling as step 1) liquid phase, and remaining part returns to washing
Tower forms circulation as washing liquid, and sodium carbonate is added in the BYD reactor as buffer.
4. the synthetic method of BED according to claim 1, which is characterized in that filter described in step 1), filtered using candle
Device filtering, it is spare into BYD collecting tank.
5. the synthetic method of BED according to claim 3, which is characterized in that the BYD solution in BYD collecting tank is preheated
Afterwards, it is pumped to formaldehyde recycle column, the Vapor phase partial at the top of the formaldehyde recycle column is used as step 1) liquid phase, remaining part through condensation
After cooling into condensation by contact tower, lime set is formed, lime set is divided into four parts, and first part is back to formaldehyde circulation tower top, with
After being pumped to the BYD solution heat exchange in formaldehyde recycle column, purification BYD is obtained, second part is as step 1) liquid phase, Part III
After cooling, condensation by contact tower is returned as spray liquid, and Part IV returns to scrubbing tower as washing liquid.
6. the synthetic method of BED according to claim 1, which is characterized in that catalyst described in step 3) is Raney's nickel.
7. the synthetic method of BED according to claim 1, which is characterized in that the step 4) dehydrating kettle is opened matched
Vacuum system vacuumizes, and is heated up using steam, until temperature rises to 95 DEG C, dehydrating kettle vacuum degree is -0.08MPa, is warming up to 125
DEG C, close vacuum system.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110540489A (en) * | 2019-09-17 | 2019-12-06 | 凯莱英生命科学技术(天津)有限公司 | method for addition reaction of acetylene and ketone compound |
| WO2021051275A1 (en) * | 2019-09-17 | 2021-03-25 | 凯莱英生命科学技术(天津)有限公司 | Method for performing addition reaction between acetylene and ketone compound |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110540489A (en) * | 2019-09-17 | 2019-12-06 | 凯莱英生命科学技术(天津)有限公司 | method for addition reaction of acetylene and ketone compound |
| WO2021051275A1 (en) * | 2019-09-17 | 2021-03-25 | 凯莱英生命科学技术(天津)有限公司 | Method for performing addition reaction between acetylene and ketone compound |
| KR20220065015A (en) * | 2019-09-17 | 2022-05-19 | 아심켐 라이프 사이언스 (톈진) 컴퍼니, 리미티드 | Addition reaction method of acetylene and ketone-based compounds |
| CN110540489B (en) * | 2019-09-17 | 2022-09-02 | 凯莱英生命科学技术(天津)有限公司 | Method for addition reaction of acetylene and ketone compound |
| KR102656545B1 (en) | 2019-09-17 | 2024-04-09 | 아심켐 라이프 사이언스 (톈진) 컴퍼니, 리미티드 | Addition reaction method of acetylene and ketone compounds |
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Application publication date: 20190524 |