CN104230678A - Method for producing dipropylene glycol butyl ether and tripropylene glycol butyl ether - Google Patents
Method for producing dipropylene glycol butyl ether and tripropylene glycol butyl ether Download PDFInfo
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- CN104230678A CN104230678A CN201410455612.XA CN201410455612A CN104230678A CN 104230678 A CN104230678 A CN 104230678A CN 201410455612 A CN201410455612 A CN 201410455612A CN 104230678 A CN104230678 A CN 104230678A
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- butyl ether
- glycol butyl
- tripropylene glycol
- tower
- alcohol
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- RNFAKTRFMQEEQE-UHFFFAOYSA-N Tripropylene glycol butyl ether Chemical compound CCCCOC(CC)OC(C)COC(O)CC RNFAKTRFMQEEQE-UHFFFAOYSA-N 0.000 title claims abstract description 91
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 135
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 81
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000047 product Substances 0.000 claims abstract description 38
- 150000003839 salts Chemical class 0.000 claims abstract description 28
- 229940039790 sodium oxalate Drugs 0.000 claims abstract description 28
- IDQBJILTOGBZCR-UHFFFAOYSA-N 1-butoxypropan-1-ol Chemical compound CCCCOC(O)CC IDQBJILTOGBZCR-UHFFFAOYSA-N 0.000 claims abstract description 27
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 27
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims abstract description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000009835 boiling Methods 0.000 claims abstract description 23
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 230000007935 neutral effect Effects 0.000 claims abstract description 3
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 43
- 239000003153 chemical reaction reagent Substances 0.000 claims description 42
- 238000000605 extraction Methods 0.000 claims description 39
- 239000007795 chemical reaction product Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- -1 2-butoxy-1-propyl Chemical group 0.000 claims description 26
- 239000013078 crystal Substances 0.000 claims description 23
- 229910001220 stainless steel Inorganic materials 0.000 claims description 21
- 239000010935 stainless steel Substances 0.000 claims description 21
- 238000010992 reflux Methods 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000012546 transfer Methods 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 13
- 239000003513 alkali Substances 0.000 claims description 12
- 238000001514 detection method Methods 0.000 claims description 11
- 238000004821 distillation Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 7
- 238000004458 analytical method Methods 0.000 claims description 6
- 239000004744 fabric Substances 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 230000000717 retained effect Effects 0.000 claims description 4
- 238000002479 acid--base titration Methods 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 230000001276 controlling effect Effects 0.000 claims description 3
- 239000000498 cooling water Substances 0.000 claims description 3
- 230000001186 cumulative effect Effects 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 210000002784 stomach Anatomy 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000012360 testing method Methods 0.000 claims description 3
- 238000004448 titration Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 2
- 238000009288 screen filtration Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 5
- 238000005406 washing Methods 0.000 abstract description 4
- WGKZYJXRTIPTCV-UHFFFAOYSA-N 2-butoxypropan-1-ol Chemical compound CCCCOC(C)CO WGKZYJXRTIPTCV-UHFFFAOYSA-N 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract 2
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 abstract 1
- 206010011469 Crying Diseases 0.000 abstract 1
- 238000007259 addition reaction Methods 0.000 abstract 1
- 238000007142 ring opening reaction Methods 0.000 abstract 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 63
- 238000000576 coating method Methods 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 239000004902 Softening Agent Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000001988 toxicity Effects 0.000 description 4
- 231100000419 toxicity Toxicity 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- WMDZKDKPYCNCDZ-UHFFFAOYSA-N 2-(2-butoxypropoxy)propan-1-ol Chemical group CCCCOC(C)COC(C)CO WMDZKDKPYCNCDZ-UHFFFAOYSA-N 0.000 description 1
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 description 1
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 description 1
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical class COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 206010003694 Atrophy Diseases 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000012675 alcoholic extract Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000037444 atrophy Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 210000003563 lymphoid tissue Anatomy 0.000 description 1
- 210000001161 mammalian embryo Anatomy 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000007170 pathology Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
- C07C41/42—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
Abstract
The invention discloses a method for producing dipropylene glycol butyl ether and tripropylene glycol butyl ether. The method creatively comprises the following steps: by taking tower bottom obtained after propanediol butyl ether is extracted as a raw material, performing ring-opening addition reaction with epoxypropane under the action of a strong-basicity catalyst, recycling excessive 2-butoxyl-1-propanol in a synthesis product, and rectifying to obtain a dipropylene glycol butyl ether product; then neutralizing the alcohol-ether solution obtained after propanediol butyl ether is extracted to be neutral with oxalic acid, filtering out generated sodium oxalate through a screen, rectifying and separating light components, and distilling to obtain a tripropylene glycol butyl ether product; then washing wet salt with methanol, rectifying the methanol solution, and recycling sodium oxalate and methanol, to obtain alcohol ether with high boiling point and realize clean production. The byproduct 2-butoxyl-1-propanol which is generated during production of propylene glycol butyl ether and is not popular with a downstream market is converted into environment-friendly solvents such as dipropylene glycol butyl ether and tripropylene glycol butyl ether which are crying needs by downstream enterprises.
Description
Technical field
The present invention relates to a kind of method of producing dipropylene and tripropylene glycol butyl ether, belong to the cleaner production field of organic solvent.
Background technology
Both containing alcoholic extract hydroxyl group in alcohol ether product, again containing ehter bond, it is the field of new such as coating and ink application solvent very widely.Although the starting of propylene glycol product is later than glycol ether product, but from nineteen eighty-two Europe chemical industry and the toxicity research delivered about glycol ether product of toxicity center report, point out that glycol ether product all has toxicity in various degree to the marrow of animal, Lymphoid tissue and embryo, after the pathology of blood can be caused, glycol ether product receives the restriction of some rule and standard both at home and abroad, and its output is in progressively atrophy.
Because several years ago glycol ether series products is classified as by forms such as REACH regulations the material (SVHC) that need show great attention to by European Union area, China is also with GB24408-2009 " in exterior coating for building limits of harmful substances ", the form of the compulsory standards such as GB24409-2009 " in car paint limits of harmful substances " and GB24410 " in indoor decorating and refurnishing materials water-borne wood coating limits of harmful substances " is for building external paint, the objectionable impuritiess such as the glycol ether in car paint and water-borne wood coating propose limitation requirement, glycol ether product is used in restriction both at home and abroad so general.
And similar nature but the product of the far low propylene glycol series of toxicity just obtain and develop faster with it, except the product of dipropylene glycol methyl ether, tripropylene glycol methyl ether series, dipropylene, tripropylene glycol butyl ether are because have higher boiling range, volatilize slower, smell is very light, so the parent being more subject to the industry such as coating, cleaning formulator looks at.Dipropylene and tripropylene glycol butyl ether have good solvability to multiple novel materials such as water based emulsion, softening agent, acrylic resin, epoxy resin and urethane resins, can be used as true solvent in fields, downstream such as coating, ink and dyestuffs.Dipropylene and tripropylene glycol butyl ether also have a lot of application in metal, kitchen tackle, grease clean-out system field.
Produce propandiol butyl ether to need to use propylene oxide.Propylene oxide does not have selectivity when open loop unlike oxyethane, in its open loop addition after butanols, can form isomers:
As above, PO is the code name of propylene oxide to the reaction equation of butanols and propylene oxide.
Propandiol butyl ether is exactly 1-butoxy-2-propyl alcohol, is a kind of uncle's ether.Even and if catalyst choice obtains good again, reaction conditions controls appropriate, stable again, always also can generate 2-butoxy-1-propyl alcohol after some propylene oxide addition while generation propandiol butyl ether, it is a kind of secondary ether.Along with the raising of modern separation technology level, 1-butoxy-2-propyl alcohol and 2-butoxy-1-propyl alcohol are separated, so be not particularly point out, propandiol butyl ether is not the mixture of above-mentioned two kinds of isomerss, but specially refers to 1-butoxy-2-propyl alcohol.
Although this secondary ether has similar physical properties and solubility property with uncle's ether, be but out of favour at Downstream Market.This byproduct will account for about 2% of product total amount in propandiol butyl ether production process.It cannot be retained in tower bottoms and go process as waste water.And, in the reaction process of propylene oxide and butanols, also can form the tripropylene glycol butyl ether of some dipropylene and minute quantity.When the dipropylene of tower bottoms will be extracted, must first 2-butoxy-1-propanol extraction lower for boiling point out, and the 2-butoxy-1-propyl alcohol extracted does not have any marketable value, will consume the energy on the contrary.
Thus will find reasonable approach, be useful composition unwelcome conversion, then be product by these useful conversions, while meeting downstream user demand, for enterprise wins income.
Erect image butanols and propylene oxide carry out opening, and to generate two kinds of isomerss the same, tower bottoms containing propandiol butyl ether and 2-butoxy-1-propyl alcohol carries out second-order opening with propylene oxide again, the just each self-generating of energy two isomerss, symbiosis becomes the isomers of four second orders.They just form dipropylene, and English name is Dipropylene Glycol n-Butyl Ether, and English abbreviation is DPnB, and the boiling range under normal pressure is 215 ~ 245 DEG C.When indicating especially, the combination of what " dipropylene " referred to is exactly four isomerss.
These four isomerss are also had an opportunity and propylene oxide in reaction system carries out the open loop addition on three rank again, and each self-generating two isomerss, symbiosis becomes eight three rank isomerss.They are composition tripropylene glycol butyl ether just, and its English name is: Tripropylene Glycol n-Butyl Ether, and English abbreviation is TPnB, and the boiling range under normal pressure is 260 ~ 295 DEG C.When indicating especially, the combination of what " tripropylene glycol butyl ether " referred to is exactly eight isomerss.
If can allow the tower bottoms after having extracted propandiol butyl ether again with propylene oxide reaction once, wherein unwelcome 2-butoxy-1-propyl alcohol is just converted at the very useful dipropylene of Downstream Market and tripropylene glycol butyl ether product without purifying in advance, significantly promote the output of dipropylene, these useful products of tripropylene glycol butyl ether, just can severally at one stroke obtain, realization is turned waste into wealth, energy-saving and emission-reduction.
Because the strong alkali catalyst adopted when current continuous processing produces propandiol butyl ether is generally sodium methylate, be enriched sodium methylate so extracted in the tower bottoms after propandiol butyl ether.Sodium methylate can decomposite methyl alcohol under the high temperature conditions, and after the material ingress of air in rectifying still, methyl alcohol and air can form explosion gas, if so tower bottoms or the raffinate containing sodium methylate are steamed too dry, be easy to cause Peril Incident.
And sodium methylate is have well deliquescent in alcohol ethers solution, by filters, sodium methylate can not be removed.In order to solve the hidden danger of this respect, in considering to come with a kind of acid and sodium methylate, producing the salt that solubleness in alcohol ether is little, being unlikely to again the additional cost because selecting very expensive acid to cause increase too many, again rectifying is carried out to the alcohol ethereal solution filtering out salt, therefrom extract tripropylene glycol butyl ether.
For the deficiency of industry when producing dipropylene and tripropylene glycol butyl ether in the processing method that exists and the difficult problem such as sodium methylate how processing enrichment in tower bottoms, be necessary a kind of method developing cleaner production dipropylene and tripropylene glycol butyl ether, 2-butoxy-1-the propyl alcohol in the tower bottoms after the complete propandiol butyl ether of extraction can either be made to be converted into dipropylene, these materials useful in downstream of tripropylene glycol butyl ether, the salt of generation can be removed again by specific way, reclaim out sodium oxalate, allow specialty factory return home use production oxalic acid, realize cleaning of whole production process.
Summary of the invention
The object of the invention is to for deficiency of the prior art, a kind of method of producing dipropylene and tripropylene glycol butyl ether is provided, the massfraction sum of dipropylene four kinds of isomerss and tripropylene glycol butyl ether eight kinds of isomerss can reach more than 95.0%, can meet the service requirements to dipropylene and tripropylene glycol butyl ether of downstream water based emulsion, softening agent, coating, ink and clean-out system industry.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of method of producing dipropylene and tripropylene glycol butyl ether, its innovative point is: be raw material with having extracted the tower bottoms after propandiol butyl ether, under the effect of strong alkali catalyst, opening is carried out with propylene oxide, after reclaiming 2-butoxy-1-propyl alcohol excessive in synthetic product, rectifying goes out dipropylene product; Subsequently with extremely neutral with the alcohol ethereal solution extracted after dipropylene in oxalic acid, the oxalic acid sodium salt falling to generate with screen filtration, after rectifying separation light constituent, distills out tripropylene glycol butyl ether product; Wash wet salt with methyl alcohol again, rectifying is carried out to methanol solution, reclaim out sodium oxalate and methyl alcohol, and obtain high boiling alcohol ether.
Further, concrete production stage is as follows:
(1) massfraction of water in the tower bottoms of the complete propandiol butyl ether of extraction being used as raw material is first measured by karl Fischer Moisture Meter; Secondly with the massfraction of the sodium methylate in the volumetric determination tower bottoms of acid base titration; Then analyzing on gas chromatograph with the strong polarity capillary chromatographic column of FFAP can by the area percentage of the component of gas chromatographic detection in tower bottoms, after being multiplied by (massfraction of the massfraction-sodium methylate of 1-water) such coefficient, obtaining tower bottoms can by the massfraction of the component of gas chromatographic detection;
(2) with the tower bottoms be detected in step (1) and propylene oxide under the effect of strong alkali catalyst, in withstand voltage reactor, with 100 ~ 200 DEG C, 2 ~ 10kgf/cm
2condition under reaction 0.5 ~ 5h; Wherein, the ratio of the component propandiol butyl ether in propylene oxide molar weight and tower bottoms and the molar weight sum of 2-butoxy-1-propyl alcohol is 1.0 ~ 1.5:1, and the propandiol butyl ether in the molar weight of the strong alkali catalyst of interpolation and tower bottoms and the ratio of 2-butoxy-1-propyl alcohol molar weight sum are 0.005 ~ 0.05:1;
(3)-0.09MPa is less than at pressure, still temperature is 78 ~ 88 DEG C, hypomere tower joint temperature is 70 ~ 80 DEG C, epimere tower joint temperature is 61 ~ 71 DEG C, tower top temperature is 52 ~ 66 DEG C, extraction reflux ratio is under the condition of 1:2 ~ 2:1, reclaims out 2-butoxy-1-propyl alcohol excessive in reaction solution by rectifying;
(4) condition of regulating step (3), control pressure is less than-0.09MPa, still temperature is 120 ~ 148 DEG C, hypomere tower joint temperature is 115 ~ 138 DEG C, epimere tower joint temperature is 90 ~ 113 DEG C, tower top temperature is 85 ~ 108 DEG C, extraction reflux ratio is under the condition of 1 ︰ 2 ~ 2 ︰ 1, by rectifying extraction dipropylene product;
(5) after the salvage stores cool to room temperature in the step (4) in rectifying still, to transfer to a volume be in the ground reagent bottle of 5L by residual for the still in rectifying still, and accumulate 3 ~ 6 batches, to have extracted the still after dipropylene residual, until the volume accumulated is more than 3L;
(6) reagent bottle holding alcohol ethereal solution is stirred with splash bar, when being stirred to dissolution homogeneity, therefrom take out 10mL sample with in the transfer pipet of 10mL, measure the basicity of this alcohol ethereal solution with the Hydrochloric Standard Titration of 0.010 ± 0.002mol/L, wherein, the H consumed is needed with the test portion of unit mass
2c
2o
42H
2the milligram number of O represents the basicity of alcohol ethereal solution, calculates the quality of the oxalic acid crystal needed for the basic catalyst in neutralized alcohol ethereal solution after the basicity of alcohol ethereal solution being multiplied with the quality of the alcohol ethereal solution that will be processed;
(7) the oxalic acid crystal of calculated mass is divided into 5 parts by quality, with pan paper on electronic weighing scale successively precise go out, then in the ground reagent bottle of dress alcohol ethereal solution, the oxalic acid crystal of calculated mass is added by part, often add portion, 10 ~ 30 times alcohol ethereal solutions are stirred, until the oxalic acid crystal of calculated mass all adds with splash bar;
(8) be put in Büchner funnel with 400 object stainless steel meshs, Büchner funnel is placed on filter flask, with the salt-containing liquid in splash bar whipping step (7) reagent bottle, when the small-particle observing sodium oxalate rises, material in reagent bottle is watered in stainless steel mesh carefully, equably, when screen surface is paved with one deck small-particle, open the vacuum pump connecting filter flask, the reading controlling the vacuum meter on surge flask is in-0.10 ~-0.05MPa scope, carry out decompress filter, until the salt-containing liquid in reagent bottle is all poured out;
(9) transfer in the ground reagent bottle of a 1000mL with stainless steel spoon carefully by the wet salt in step (8) screen cloth, the liquid in filter flask is retained in filter flask;
(10) by the suction filtration liquid rectification and purification tripropylene glycol butyl ether in filter flask in step (9), specifically as follows step by step:
A () neutralized reaction product analysis: sample from filter flask, first records the massfraction of water in the neutralized reaction product that will prepare rectifying by karl Fischer Moisture Meter; Secondly by calculating, calculating and neutralizing by the oxalic acid added the massfraction of sodium oxalate in neutralized reaction product obtained; Then analyzing on gas chromatograph with the strong polarity capillary chromatographic column of FFAP can by the area percentage of the component of gas chromatographic detection in neutralized reaction product, after being multiplied by (massfraction of the massfraction-sodium oxalate of 1-water) such coefficient, obtaining in neutralized reaction product can by the massfraction of the component of gas chromatographic detection, draws the volume number under the normal temperature that the tripropylene glycol butyl ether of the mass percent sum shared by eight kinds of isomerss of tripropylene glycol butyl ether in neutralized reaction product and respective quality is corresponding;
B filtrate in filter flask is transferred in rectifying still by funnel by () carefully, rectifying still is put in electric food warmer carefully, by regulating the lifting table below electric food warmer, the lower tower joint of the middle pit of the stomach of rectifying still and rectifying tower is connected, adopts the rectifying tower having pre-installed the 316L stainless steel θ ring filler of Φ 3 × 3mm to be separated neutralized reaction product;
C () carries out rectification under vacuum under the pressure of distillation system is less than the condition of-0.09MPa;
D () is 50 ~ 65 DEG C in still temperature, hypomere tower joint temperature is 45 ~ 60 DEG C, epimere tower joint temperature is 30 ~ 45 DEG C, tower top temperature is 25 ~ 40 DEG C, extraction reflux ratio is under the condition of 1:2 ~ 2:1, steam neutralizing agent the oxalic acid crystal water brought into and the methyl alcohol or the first alcohol and water that neutralize formation, treat that the volume of the low product that boils that the first alcohol and water collected in holding tank is such reaches 80% ~ 98% of volume corresponding to the quality of the so low product that boils of first alcohol and water in the neutralized reaction product calculated, simultaneously at corresponding temperature, the speed that steams of tower top is less than every 10s3 when dripping, by the water in holding tank and low product extraction of boiling, then holding tank is allowed again to be incorporated to Distallation systm for receiving, the cut that extraction is follow-up,
E () is 120 ~ 148 DEG C in still temperature, under hypomere tower joint temperature is 115 ~ 138 DEG C, epimere tower joint temperature is 90 ~ 113 DEG C, tower top temperature is 85 ~ 108 DEG C, extraction reflux ratio is the condition of 1:2 ~ 2:1, steams dipropylene cut still remaining in neutralized reaction product;
F () is 135 ~ 165 DEG C in still temperature, under hypomere tower joint temperature is 130 ~ 154 DEG C, epimere tower joint temperature is 105 ~ 130 DEG C, tower top temperature is 100 ~ 125 DEG C, extraction reflux ratio is the condition of 1:2 ~ 2:1, steams the tripropylene glycol butyl ether cut in neutralized reaction product;
(g) when the volume that capacity is the tripropylene glycol butyl ether cut collected in the holding tank of 1L reaches 800 ± 50mL, by first for this part tripropylene glycol butyl ether extraction;
H () repeats the extraction three times of (g) step by step;
(i) continue to collect the tripropylene glycol butyl ether distilled out, until the cumulative volume of the tripropylene glycol butyl ether cut steamed reach the volume corresponding for the total mass of the isomers of tripropylene glycol butyl ether in the neutralized reaction product of rectifying calculated after stratographic analysis in (a) step by step 90 ~ 99%, at corresponding temperature, the speed that steams of tower top is less than every 10s5 when dripping simultaneously, close the heater switch of tower bottom of rectifying tower, each section of tower joint, the tripropylene glycol butyl ether transfer in holding tank is merged into and puts in the ground reagent bottle of tripropylene glycol butyl ether;
J () is collected in one posts in the reagent bottle of respective labels by residual for the still in rectifying still;
(11) after rectification and purification tripropylene glycol butyl ether, add in step (9) with the methyl alcohol of 0.5 ~ 3 times of volume in stink cupboard and hold in the ground reagent bottle of wet salt, stir 10 ~ 30 minutes with splash bar;
(12) in stink cupboard, be put in Büchner funnel with 400 object stainless steel meshs, the clean beaker of a 500mL is put in the below of Büchner funnel, with the salt-containing liquid in splash bar whipping step (11) reagent bottle, when time the small-particle of sodium oxalate rises, material in reagent bottle is watered in stainless steel mesh carefully, equably, small-particle is distributed in screen surface equably, collect methanol solution with the beaker below Büchner funnel;
(13) with stainless steel spoon, the wet salt in screen cloth is carefully transferred in the beaker of 1 ~ 10 250mL equably, cover watch-glass, the filtering port of beaker is made to leave the outlet of volatilizing for methyl alcohol, be put in vacuum drying oven, be less than the pressure of-0.09MPa, reduce pressure under the temperature condition of 25 ~ 35 DEG C suction dried, then merges the crystal in each beaker, transfer in the ground reagent bottle of the 1000mL storing sodium oxalate, the methyl alcohol cooling water condensation pumped out, collection;
(14) methanol solution methyl alcohol collected in step (13) suction dried process and step (12) filtered out merges, and is collected in the ground reagent bottle of a 5L;
(15) after the volume of the methanol solution collected is more than 3L, these methanol solutions are carried out atmospheric distillation separation on distillation system, still temperature is 75 ~ 90 DEG C, hypomere tower joint temperature is 70 ~ 80 DEG C, epimere tower joint temperature is 66 ~ 73 DEG C, tower top temperature is 64 ~ 70 DEG C, extraction reflux ratio is 1:1, reclaim out the methyl alcohol that can be used for subsequent wash sodium oxalate crystal, and to eliminate the still of methyl alcohol residual through rectifying be tripropylene glycol butyl ether and the alcohol ether higher than tripropylene glycol butyl ether boiling point, and the height that in step (10), (j) obtains step by step boils the residual merging of still.
Further, described strong alkali catalyst is solid sodium methylate or solid sodium hydroxide.
Further, described strong alkali catalyst is solid sodium methylate.
Beneficial effect of the present invention is as follows:
(1) method of the present invention allow and extracted propandiol butyl ether after tower bottoms again with propylene oxide reaction once, being wherein just converted at the very useful dipropylene of Downstream Market and tripropylene glycol butyl ether product at Downstream Market unwelcome 2-butoxy-1-propyl alcohol without purifying in advance, significantly promote the output of dipropylene, these useful products of tripropylene glycol butyl ether, can severally at one stroke obtain, realization is turned waste into wealth, energy-saving and emission-reduction.
(2) dipropylene adopting the inventive method to prepare and the boiling range of tripropylene glycol butyl ether meet the requirements, through gas chromatographic analysis, the massfraction sum of dipropylene four kinds of isomerss and tripropylene glycol butyl ether eight kinds of isomerss can reach more than 95.0%, can meet the service requirements to dipropylene and tripropylene glycol butyl ether of downstream water based emulsion, softening agent, coating, ink and clean-out system industry.
(3) the present invention is due to when with tower bottoms and propylene oxide reaction synthesis dipropylene, have an appointment 20 ~ 40% dipropylene can continue to generate the higher tripropylene glycol butyl ether of boiling point with propylene oxide reaction, so adopt such synthetic method also can ensure, tripropylene glycol butyl ether has enough output, and the volume of these tripropylene glycol butyl ether is enough to dissolve sodium methylate, the catalyzer such as sodium hydroxide, after extracted the dipropylene in synthetic product by rectifying, corresponding processing temperature is still unlikely to sodium methylate is wherein decomposed, produce hidden peril of explosion.
(4) the present invention adopts oxalic acid as neutralizing agent, the solubleness of sodium oxalate crystal in alcohol ethereal solution neutralizing rear formation can be made lower, make basic catalyst can be able to be removed more fully, there will not be the solubleness of other salt in alcohol ethereal solution because adopting other acid neutralization to cause generating and concentration larger, in the process of follow-up distillation extraction tripropylene glycol butyl ether, occur that salt is brought to steam fills in Packed rectifying tower, the situation of blocking rectifying tower, and oxalic acid is also common on a kind of market, the organic acid that price is not high, can not be a lot of because of adopting this acid to make the cost producing tripropylene glycol butyl ether increase.
(5) the present invention's sodium oxalate wet salt of adopting methyl alcohol to carry out washing and filtering to obtain, the high boiling alcohol ethers such as the tripropylene glycol butyl ether of wet salt surface adsorption, four propandiol butyl ethers can be washed, after the sodium methylate suction dried after washing, the sodium oxalate that can be utilized again can also be obtained, avoid the generation of solid waste, and the separating methanol that boiling point is very low can also be fallen by the means of rectifying by the methyl alcohol-ol ethereal solution obtained after washing, the height the obtained alcohol ether that boils can also be used as the solvent of some coating, so just turn avoid the generation of waste water.Follow-up preparation is continued on for after method steps (3) 2-butoxy-1-propyl alcohol reclaimed out also can merge with having extracted the tower bottoms after propandiol butyl ether.Like this, the cleaner production of whole technological process is achieved.
Embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is elaborated.
Embodiment
Produce a method for dipropylene and tripropylene glycol butyl ether, concrete steps are as follows:
(1) first measuring certain batch of massfraction being used as the water of the tower bottoms of the complete propandiol butyl ether of extraction of raw material by karl Fischer Moisture Meter is 0.05%; Be 2.50% with the massfraction of the sodium methylate in the volumetric determination tower bottoms of acid base titration; Then analyzing on gas chromatograph with the strong polarity capillary chromatographic column of FFAP can by the area percentage of the component of gas chromatographic detection in tower bottoms, after being multiplied by (massfraction of the massfraction-sodium methylate of 1-water) such coefficient, obtaining this batch of tower bottoms can be by the massfraction of the component of gas chromatographic detection:
Propandiol butyl ether 0.45%
2-butoxy-1-propyl alcohol 23.63%
Dipropylene 68.96%
Tripropylene glycol butyl ether 3.42%
Other impurity 0.99%;
(2) tower bottoms be detected by step (1) and propylene oxide under the effect of strong alkali catalyst solid sodium methylate, in withstand voltage reactor, at 120 ~ 170 DEG C, 2 ~ 7kgf/cm
2condition under react 2.5h, wherein, propandiol butyl ether in the molar weight of propylene oxide used and tower bottoms and the ratio of 2-butoxy-1-propyl alcohol molar weight sum are 1.2 ︰ 1, and the massfraction of interpolation is the ratio of propandiol butyl ether in the molar weight of the granular sodium methoxide catalyst of 97.2% and still liquid and 2-butoxy-1-propyl alcohol molar weight sum is 0.019:1;
(3) be-0.092 ~-0.097MPa at pressure, still temperature is 80 ~ 87 DEG C, hypomere tower joint temperature is 80 ~ 87 DEG C, epimere tower joint temperature is 59 ~ 68 DEG C, tower top temperature is 54 ~ 64 DEG C, extraction reflux ratio is under the condition of 1:1, reclaims out 2-butoxy-1-propyl alcohol excessive in reaction solution by rectifying;
(4) condition of regulating step (3), be-0.092 ~-0.097MPa at pressure, still temperature is 124 ~ 145 DEG C, hypomere tower joint temperature is 119 ~ 135 DEG C, epimere tower joint temperature is 95 ~ 110 DEG C, tower top temperature is 88 ~ 105 DEG C, extraction reflux ratio is under the condition of 1:1, by rectifying extraction dipropylene product;
(5) after the salvage stores cool to room temperature in the step (4) in rectifying still, to transfer to a volume be in the ground reagent bottle of 5L by residual for the still in rectifying still, and accumulating 4 batches, to have extracted the still after dipropylene residual, and the volume of accumulation reaches 3.5L;
(6) stir the reagent bottle holding alcohol ethereal solution with splash bar, when being stirred to dissolution homogeneity, therefrom take out 10mL sample with in the transfer pipet of 10mL, use 0.01172mol/L Hydrochloric Standard Titration, the basicity recording this alcohol ethereal solution is 85.9mg H
2c
2o
42H
2o/g test portion, after the basicity of alcohol ethereal solution being multiplied with the quality 3258g of the alcohol ethereal solution that will be processed, the quality calculating the oxalic acid crystal needed for the basic catalyst in neutralized alcohol ethereal solution is 280g;
(7) the oxalic acid crystal of calculated mass is divided into 5 parts by quality, i.e. every part of 56g, go out with pan paper precise on electronic weighing scale, then in the ground reagent bottle of dress alcohol ethereal solution by the oxalic acid crystal weighed part adding, often add portion, stir 20 times alcohol ethereal solutions with splash bar, the oxalic acid crystal added can be incorporated in alcohol ethereal solution completely, increasing sodium oxalate small-particle can have been seen separate out, until the oxalic acid crystal weighed all adds simultaneously;
(8) be put in Büchner funnel with 400 object stainless steel meshs, Büchner funnel is placed on filter flask, with the salt-containing liquid in splash bar whipping step (7) reagent bottle, when time the small-particle of sodium oxalate rises, material in reagent bottle is watered in stainless steel mesh carefully, equably, when screen surface is paved with one deck small-particle, open the vacuum pump connecting filter flask, the reading controlling the vacuum meter on surge flask is-0.09MPa, carry out decompress filter, until the salt-containing liquid in reagent bottle is all poured out;
(9) transfer in the ground reagent bottle of a 1000mL with stainless steel spoon carefully by the wet salt in step (8) screen cloth, the liquid in filter flask is retained in filter flask;
(10) by the suction filtration liquid rectification and purification tripropylene glycol butyl ether in filter flask in step (9), be step by step specifically:
(a) neutralized reaction product analysis: sample from filter flask, the massfraction recording water in the neutralized reaction product that will prepare rectifying by karl Fischer Moisture Meter is 0.05%; By calculating, calculating and neutralizing by the oxalic acid added the massfraction of sodium oxalate in neutralized reaction product obtained is 8.41%; Then use the strong polarity capillary chromatographic column of FFAP of 25m × 0.32mm × 0.5 μm on gas chromatograph, analyze the area percentage of the component that can be detected by chromatogram in neutralized reaction product, after being multiplied by (massfraction of the massfraction-sodium oxalate of 1-water) such coefficient, obtaining can by the massfraction of the component of gas chromatographic detection in this batch of neutralized reaction product, the mass percent sum shared by eight kinds of isomerss drawing tripropylene glycol butyl ether in neutralized reaction product is 74.37%, and the volume number under normal temperature corresponding to the tripropylene glycol butyl ether of respective quality is 2605mL;
B filtrate in filter flask is transferred in rectifying still by funnel by () carefully, rectifying still is put in electric food warmer carefully, by regulating the lifting table below electric food warmer, the lower tower joint of the middle pit of the stomach of rectifying still and rectifying tower is connected, adopt the rectifying tower of following specification to distill neutralized reaction product: rectifying tower hypomere tower joint is Φ 35 × 800mm, epimere tower joint is Φ 35 × 500mm, has all loaded the 316L stainless steel θ ring filler of Φ 3 × 3mm in two sections of tower joints;
C () carries out rectification under vacuum under the pressure of distillation system is the condition of-0.095MPa;
D () is 53 ~ 62 DEG C in still temperature, hypomere tower joint temperature is 48 ~ 56 DEG C, epimere tower joint temperature is 35 ~ 42 DEG C, tower top temperature is 28 ~ 38 DEG C, extraction reflux ratio is under the condition of 1:1, steam the crystal water that neutralizing agent oxalic acid is brought into and the methyl alcohol neutralizing formation, volume Deng the such low product that boils of the first alcohol and water collected in holding tank reaches 210mL, reach 82% of volume 256mL corresponding to the quality of the so low product that boils of first alcohol and water in the neutralized reaction product calculated, when at corresponding temperature, the speed that steams of tower top only has every 10s1 ~ 2 droplet, by the water in holding tank and low product extraction of boiling, then holding tank is allowed again to be incorporated to Distallation systm for receiving, the cut that extraction is follow-up,
E () is 124 ~ 145 DEG C in still temperature, under hypomere tower joint temperature is 119 ~ 135 DEG C, epimere tower joint temperature is 95 ~ 110 DEG C, tower top temperature is 88 ~ 105 DEG C, extraction reflux ratio is the condition of 1 ︰ 1, steams dipropylene cut still remaining in neutralized reaction product;
F () is 138 ~ 162 DEG C in still temperature, under hypomere tower joint temperature is 134 ~ 150 DEG C, epimere tower joint temperature is 110 ~ 126 DEG C, tower top temperature is 103 ~ 123 DEG C, extraction reflux ratio is the condition of 1:1, steams the tripropylene glycol butyl ether cut in neutralized reaction product;
(g) when the volume that capacity is the tripropylene glycol butyl ether cut collected in the holding tank of 1L reaches 800 ± 50mL, by first for this part tripropylene glycol butyl ether extraction;
H () repeats the extraction three times of (g) step by step, obtain the tripropylene glycol butyl ether 2.4L in the neutralized reaction product of this batch of distillation;
(i) continue to collect the tripropylene glycol butyl ether distilled out, until the cumulative volume of the tripropylene glycol butyl ether cut steamed reaches 2554mL, this batch calculated after reaching (a) stratographic analysis is step by step for 98% of volume 2605mL corresponding to the total mass of several isomerss of tripropylene glycol butyl ether in the neutralized reaction product of rectifying, when simultaneously at corresponding temperature, the speed that steams of tower top only has every 10s2 ~ 3 droplet, close tower bottom of rectifying tower, the heater switch of each section of tower joint, by the tripropylene glycol butyl ether transfer in holding tank, be merged into and put in the ground reagent bottle of tripropylene glycol butyl ether,
J () is collected in one posts in the reagent bottle of " height boil still residual " label by residual for the still in rectifying still;
(11), after rectification and purification tripropylene glycol butyl ether, add in step (9) with the methyl alcohol of 1.5 times of volumes in stink cupboard and hold in the ground reagent bottle of wet salt, stir 20 minutes with splash bar;
(12) in stink cupboard, be put in Büchner funnel with 400 object stainless steel meshs, the clean beaker of a 500mL is put in the below of Büchner funnel, with the salt-containing liquid in splash bar whipping step (11) reagent bottle, when time the small-particle of sodium oxalate rises, material in reagent bottle is watered in stainless steel mesh carefully, equably, small-particle is distributed in screen surface equably;
(13) with stainless steel spoon, the wet salt in screen cloth is carefully transferred in the beaker of 8 250mL equably, cover watch-glass, the filtering port of beaker is made to leave the outlet of volatilizing for methyl alcohol, be put in vacuum drying oven, at the pressure of-0.095MPa, reduce pressure under the temperature condition of 28 ~ 32 DEG C suction dried, then merges the crystal in each beaker, transfer in the ground reagent bottle of the 1000mL storing sodium oxalate, the methyl alcohol cooling water condensation pumped out, collection;
(14) methanol solution methyl alcohol collected in step (13) suction dried process and step (12) filtered out merges, and is collected in the ground reagent bottle of a 5L;
(15) after the volume of the methanol solution collected is more than 3L, these methanol solutions are carried out atmospheric distillation separation on distillation system, still temperature is 78 ~ 88 DEG C, hypomere tower joint temperature is 72 ~ 78 DEG C, epimere tower joint temperature is 67 ~ 72 DEG C, tower top temperature is 64.5 ~ 69 DEG C, extraction reflux ratio is 1:1, reclaim out the methyl alcohol that can be used for subsequent wash sodium oxalate crystal, and to eliminate the still of methyl alcohol residual through rectifying be tripropylene glycol butyl ether and the alcohol ether higher than tripropylene glycol butyl ether boiling point, and the height that in step (10), (j) obtains step by step boils the residual merging of still.
Produce and terminate, the high boiling point still obtained in later stage the present embodiment is residual be can be used for less demanding coatings enterprises as the slow solvent that volatilizees, and the massfraction of dried sodium oxalate is 99.3%, can supply oxalic acid manufacturing enterprise and go to produce oxalic acid.
Verification step: with the strong polarity capillary chromatographic column of FFAP, the massfraction sum that gas chromatograph is analyzed four isomerss of obtained dipropylene is 96.8%, and the massfraction sum of tripropylene glycol butyl ether eight isomerss is 96.3%.
Get 100 mL dipropylene samples, the boiling range measuring dipropylene with the special purpose device surveying boiling range is 218.2 ~ 240.8 DEG C.
Get 100 mL tripropylene glycol butyl ether samples, the boiling range measuring tripropylene glycol butyl ether with the special purpose device surveying boiling range is 263.7 ~ 293.5 DEG C.
The dipropylene adopting the present embodiment method to prepare and the boiling range of tripropylene glycol butyl ether all meet the requirements, through gas chromatographic analysis, the massfraction sum of dipropylene four isomers sums, tripropylene glycol butyl ether eight kinds of isomerss all reaches more than 95.0%, can meet the service requirements to dipropylene and tripropylene glycol butyl ether of downstream water based emulsion, softening agent, coating, ink and clean-out system industry.
Claims (4)
1. produce the method for dipropylene and tripropylene glycol butyl ether for one kind, it is characterized in that: be raw material with having extracted the tower bottoms after propandiol butyl ether, under the effect of strong alkali catalyst, opening is carried out with propylene oxide, after reclaiming 2-butoxy-1-propyl alcohol excessive in synthetic product, rectifying goes out dipropylene product; Subsequently with extremely neutral with the alcohol ethereal solution extracted after dipropylene in oxalic acid, the oxalic acid sodium salt falling to generate with screen filtration, after rectifying separation light constituent, distills out tripropylene glycol butyl ether product; Wash wet salt with methyl alcohol again, rectifying is carried out to methanol solution, reclaim out sodium oxalate and methyl alcohol, and obtain high boiling alcohol ether.
2. the method for production dipropylene according to claim 1 and tripropylene glycol butyl ether, is characterized in that: the method concrete steps of described production dipropylene and tripropylene glycol butyl ether are as follows:
First the massfraction of water in the tower bottoms of the complete propandiol butyl ether of extraction being used as raw material is measured by karl Fischer Moisture Meter; Secondly with the massfraction of the sodium methylate in the volumetric determination tower bottoms of acid base titration; Then analyzing on gas chromatograph with the strong polarity capillary chromatographic column of FFAP can by the area percentage of the component of gas chromatographic detection in tower bottoms, be multiplied by difference after the massfraction of the massfraction-sodium methylate of 1-water as coefficient after, obtaining tower bottoms can by the massfraction of gas chromatographic detection component;
With the tower bottoms be detected in step (1) and propylene oxide under the effect of strong alkali catalyst, in withstand voltage reactor, with 100 ~ 200 DEG C, 2 ~ 10kgf/cm
2condition under reaction 0.5 ~ 5h; Wherein, the ratio of the component propandiol butyl ether in propylene oxide molar weight and tower bottoms and the molar weight sum of 2-butoxy-1-propyl alcohol is 1.0 ~ 1.5 ︰ 1, and the propandiol butyl ether in the molar weight of the strong alkali catalyst of interpolation and tower bottoms and the ratio of 2-butoxy-1-propyl alcohol molar weight sum are 0.005 ~ 0.05:1;
-0.09MPa is less than at pressure, still temperature is 78 ~ 88 DEG C, hypomere tower joint temperature is 70 ~ 80 DEG C, epimere tower joint temperature is 61 ~ 71 DEG C, tower top temperature is 52 ~ 66 DEG C, extraction reflux ratio is under the condition of 1:2 ~ 2:1, reclaims out 2-butoxy-1-propyl alcohol excessive in reaction solution by rectifying;
The condition of regulating step (3), control pressure is less than-0.09MPa, still temperature is 120 ~ 148 DEG C, hypomere tower joint temperature is 115 ~ 138 DEG C, epimere tower joint temperature is 90 ~ 113 DEG C, tower top temperature is 85 ~ 108 DEG C, extraction reflux ratio is under the condition of 1:2 ~ 2:1, by rectifying extraction dipropylene product;
After salvage stores cool to room temperature in the step (4) in rectifying still, to transfer to a volume be in the ground reagent bottle of 5L by residual for the still in rectifying still, and accumulate 3 ~ 6 batches, to have extracted the still after dipropylene residual, until the volume accumulated is more than 3L;
The reagent bottle holding alcohol ethereal solution is stirred with splash bar, when being stirred to dissolution homogeneity, therefrom take out 10mL sample with in the transfer pipet of 10mL, measure the basicity of this alcohol ethereal solution with the Hydrochloric Standard Titration of 0.010 ± 0.002mol/L, wherein, the H consumed is needed with the test portion of unit mass
2c
2o
42H
2the milligram number of O represents the basicity of alcohol ethereal solution, calculates the quality of the oxalic acid crystal needed for the basic catalyst in neutralized alcohol ethereal solution after the basicity of alcohol ethereal solution being multiplied with the quality of the alcohol ethereal solution that will be processed;
The oxalic acid crystal of calculated mass is divided into 5 parts by quality, with pan paper on electronic weighing scale successively precise go out, then in the ground reagent bottle of dress alcohol ethereal solution, the oxalic acid crystal of calculated mass is added by part, often add portion, 10 ~ 30 times alcohol ethereal solutions are stirred, until the oxalic acid crystal of calculated mass all adds with splash bar;
Be put in Büchner funnel with 400 object stainless steel meshs, Büchner funnel is placed on filter flask, with the salt-containing liquid in splash bar whipping step (7) reagent bottle, when the small-particle observing sodium oxalate rises, material in reagent bottle is watered in stainless steel mesh carefully, equably, when screen surface is paved with one deck small-particle, open the vacuum pump connecting filter flask, the reading controlling the vacuum meter on surge flask is in-0.10 ~-0.05MPa scope, carry out decompress filter, until the salt-containing liquid in reagent bottle is all poured out;
Transfer in the ground reagent bottle of a 1000mL with stainless steel spoon carefully by the wet salt in step (8) screen cloth, the liquid in filter flask is retained in filter flask;
By the suction filtration liquid rectification and purification tripropylene glycol butyl ether in filter flask in step (9), specifically as follows step by step:
A () neutralized reaction product analysis: sample from filter flask, first records the massfraction of water in the neutralized reaction product that will prepare rectifying by karl Fischer Moisture Meter; Secondly by calculating, calculating and neutralizing by the oxalic acid added the massfraction of sodium oxalate in neutralized reaction product obtained; Then analyzing on gas chromatograph with the strong polarity capillary chromatographic column of FFAP can by the area percentage of the component of gas chromatographic detection in neutralized reaction product, be multiplied by difference after the massfraction of the massfraction-sodium oxalate of 1-water as coefficient after, obtaining in neutralized reaction product can by the massfraction of the component of gas chromatographic detection, draws the volume number under the normal temperature that the tripropylene glycol butyl ether of the mass percent sum shared by eight kinds of isomerss of tripropylene glycol butyl ether in neutralized reaction product and respective quality is corresponding;
B filtrate in filter flask is transferred in rectifying still by funnel by () carefully, rectifying still is put in electric food warmer carefully, by regulating the lifting table below electric food warmer, the lower tower joint of the middle pit of the stomach of rectifying still and rectifying tower is connected, adopts the rectifying tower having pre-installed the 316L stainless steel θ ring filler of Φ 3 × 3mm to be separated neutralized reaction product;
C () carries out rectification under vacuum under the pressure of distillation system is less than the condition of-0.09MPa;
D () is 50 ~ 65 DEG C in still temperature, hypomere tower joint temperature is 45 ~ 60 DEG C, epimere tower joint temperature is 30 ~ 45 DEG C, tower top temperature is 25 ~ 40 DEG C, extraction reflux ratio is under the condition of 1:2 ~ 2:1, steam neutralizing agent the oxalic acid crystal water brought into and the methyl alcohol or the first alcohol and water that neutralize formation, treat that the volume of the low product that boils that the first alcohol and water collected in holding tank is such reaches 80 ~ 98% of volume corresponding to the quality of the so low product that boils of first alcohol and water in the neutralized reaction product calculated, simultaneously at corresponding temperature, the speed that steams of tower top is less than every 10s3 when dripping, by the water in holding tank and low product extraction of boiling, then holding tank is allowed again to be incorporated to Distallation systm for receiving, the cut that extraction is follow-up,
E () is 120 ~ 148 DEG C in still temperature, under hypomere tower joint temperature is 115 ~ 138 DEG C, epimere tower joint temperature is 90 ~ 113 DEG C, tower top temperature is 85 ~ 108 DEG C, extraction reflux ratio is the condition of 1:2 ~ 2:1, steams dipropylene cut still remaining in neutralized reaction product;
F () is 135 ~ 165 DEG C in still temperature, under hypomere tower joint temperature is 130 ~ 154 DEG C, epimere tower joint temperature is 105 ~ 130 DEG C, tower top temperature is 100 ~ 125 DEG C, extraction reflux ratio is the condition of 1:2 ~ 2:1, steams the tripropylene glycol butyl ether cut in neutralized reaction product;
(g) when the volume that capacity is the tripropylene glycol butyl ether cut collected in the holding tank of 1L reaches 800 ± 50mL, by first for this part tripropylene glycol butyl ether extraction;
H () repeats the extraction three times of (g) step by step;
(i) continue to collect the tripropylene glycol butyl ether distilled out, until the cumulative volume of the tripropylene glycol butyl ether cut steamed reach the volume corresponding for the total mass of the isomers of tripropylene glycol butyl ether in the neutralized reaction product of rectifying calculated after stratographic analysis in (a) step by step 90 ~ 99%, at corresponding temperature, the speed that steams of tower top is less than every 10s5 when dripping simultaneously, close the heater switch of tower bottom of rectifying tower, each section of tower joint, the tripropylene glycol butyl ether transfer in holding tank is merged into and puts in the ground reagent bottle of tripropylene glycol butyl ether;
J () is collected in one posts in the reagent bottle of respective labels by residual for the still in rectifying still;
(11) after rectification and purification tripropylene glycol butyl ether, add in step (9) with the methyl alcohol of 0.5 ~ 3 times of volume in stink cupboard and hold in the ground reagent bottle of wet salt, stir 10 ~ 30 minutes with splash bar;
(12) in stink cupboard, be put in Büchner funnel with 400 object stainless steel meshs, the clean beaker of a 500mL is put in the below of Büchner funnel, with the salt-containing liquid in splash bar whipping step (11) reagent bottle, when time the small-particle of sodium oxalate rises, material in reagent bottle is watered in stainless steel mesh carefully, equably, small-particle is distributed in screen surface equably, collect methanol solution with the beaker below Büchner funnel;
(13) with stainless steel spoon, the wet salt in screen cloth is carefully transferred in the beaker of 1 ~ 10 250mL equably, cover watch-glass, the filtering port of beaker is made to leave the outlet of volatilizing for methyl alcohol, be put in vacuum drying oven, be less than the pressure of-0.09MPa, reduce pressure under the temperature condition of 25 ~ 35 DEG C suction dried, then merges the crystal in each beaker, transfer in the ground reagent bottle of the 1000mL storing sodium oxalate, the methyl alcohol cooling water condensation pumped out, collection;
(14) methanol solution methyl alcohol collected in step (13) suction dried process and step (12) filtered out merges, and is collected in the ground reagent bottle of a 5L;
(15) after the volume of the methanol solution collected is more than 3L, these methanol solutions are carried out atmospheric distillation separation on distillation system, still temperature is 75 ~ 90 DEG C, hypomere tower joint temperature is 70 ~ 80 DEG C, epimere tower joint temperature is 66 ~ 73 DEG C, tower top temperature is 64 ~ 70 DEG C, extraction reflux ratio is 1:1, reclaim out the methyl alcohol that can be used for subsequent wash sodium oxalate crystal, and to eliminate the still of methyl alcohol residual through rectifying be tripropylene glycol butyl ether and the alcohol ether higher than tripropylene glycol butyl ether boiling point, and the height that in step (10), (j) obtains step by step boils the residual merging of still.
3. the method for production dipropylene according to claim 1 and 2 and tripropylene glycol butyl ether, is characterized in that: described strong alkali catalyst is solid sodium methylate or solid sodium hydroxide.
4. the method for production dipropylene according to claim 1 and 2 and tripropylene glycol butyl ether, is characterized in that: described strong alkali catalyst is solid sodium methylate.
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