CN106117011A - A kind of discrimination method produces the process for purification of crude sodium formate byproduct from neopentyl glycol production - Google Patents
A kind of discrimination method produces the process for purification of crude sodium formate byproduct from neopentyl glycol production Download PDFInfo
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- CN106117011A CN106117011A CN201610432251.6A CN201610432251A CN106117011A CN 106117011 A CN106117011 A CN 106117011A CN 201610432251 A CN201610432251 A CN 201610432251A CN 106117011 A CN106117011 A CN 106117011A
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- isooctanol
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
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Abstract
The invention discloses a kind of discrimination method and produce the process for purification of crude sodium formate byproduct from neopentyl glycol production, including: by dissolving crude product, add cleaner, filter after remove impurity, gained filtrate carries out counter-current extraction with isobutylaldehyde, after gained isobutylaldehyde phase reuse to neopentyl glycol produces workshop section or reclaims isobutylaldehyde, rectification obtains highly purified neopentyl glycol, gained aqueous phase detects organic impurity content therein, as organic impurity content≤2wt%, process to obtain high-purity sodium formate, as organic impurity content ＞ 2wt%, counter-current extraction is carried out with isooctanol, gained aqueous phase carries out processing to obtain high-purity sodium formate.Present invention activated carbon and calcium dodecyl benzene sulfonate, as cleaner, extract with isobutylaldehyde isooctanol solvent pairs, simple to operate, taking a short time, removal of impurity is high, and three waste discharge is few, environmental pollution is little, achieve the effective recycling of resource, there is good practical value.
Description
Technical field
The present invention relates to a kind of discrimination method and produce the process for purification of crude sodium formate byproduct from neopentyl glycol production, be both specifically related to one
Sodium formate purification can be reclaimed again the process for purification of neopentyl glycol, belongs to technical field of fine.
Background technology
Neopentyl glycol is a kind of important industrial chemicals, mainly for the production of saturated/unsaturated polyester resin, oil-free alkyd
Esters, polyurethane foam plastics and elastomer elasticizer used by resin, PEPA and syntholube, senior lubricant
Additive and other fine chemicals.
1894, Apel and Tollens was found that neopentyl glycol first, and nineteen sixties is by u s company
First Texas Eastman realizes industrialized production, and the eighties is used widely as large industrial products.Neopentyl glycol
Being essentially all and be condensed to yield hydroxyl valeral under catalyst action by formaldehyde and isobutylaldehyde, it prepares neopentyl glycol through reduction again,
Reduction process can use discrimination method or catalytic hydrogenation method.Discrimination method is exactly that hydroxyl valeral exists at highly basic (such as sodium hydroxide) with formaldehyde
Under be reduced to neopentyl glycol, formaldehyde is oxidized to formic acid, then with alkali formed formates (sodium formate etc.), neopentyl glycol and first
After acid sodium separates, crude product is through being refining to obtain neopentyl glycol product.
Discrimination method produces neopentyl glycol many employings vaporizing extract process separation neopentyl glycol and sodium formate, i.e. neopentyl glycol, first at present
Acid sodium aqueous solution at high temperature enters steam stripping at reduced pressure tower, neopentyl glycol and superheated vapour generation steam distillation, and gas phase cools down
Obtain neopentyl glycol aqueous solution, then obtain product through dehydration, rectification under vacuum.Sodium formate supersaturation at the bottom of stripper tower separates out knot
Crystalline substance, centrifugal filtration, owing to steam stripping temperature is about 120-140 DEG C, impurity generation polymerization liquid meeting blackening in reactant liquor,
Therefore the sodium formate outward appearance obtained is brownish black crystallization, and sodium formate effective content is 85-88%, separately has 3-5% neopentyl glycol, other
Organic impurities 1%-3%, the also water of about 5-8%.
Document report is adopted and is processed sodium formate with the following method:
The industrial process thick sodium formate of by-product with the following method of mostly adopting: initially with high-temperature pressure-reduction distillation
Method from thick sodium formate, steam neopentyl glycol, then in residue add gas washing in SA production formic acid, see that patent is " from new penta
The method reclaiming neopentyl glycol in glycol byproduct sodium formate " (ZL98126104.3), " Method for
Producinghydroxypivalaldehyde and neopentyl glycol " (USP7,767,865, BASF SE) and
" Recycling Technology of Sodium Formate By-product of Neopentyl Glycol " [Zhang Shaohua, Kuang Yunfei, Li Wei. Hengyang Normal University's journal, 2006,27
(3): 53-54] etc., this technique can reclaim a small amount of neopentyl glycol, and the sodium formate after process can produce formic acid, but due to
During steaming neopentyl glycol from thick sodium formate, operation temperature is high (reaching more than 150 DEG C), and distillation time length (needs
Want 5-7 hour), some Organic substance is decomposed and polyreaction, and causing the sodium formate residue after distillation is black, Qi Zhongyou
The content of colored foreign substantially increases, and residue is made into the solution of mass fraction about 40%, and solution is black, therefore, this low
The sodium formate of quality is only used for the production of formic acid, and cannot be applied to sodium hydrosulfite and the production of other formic acid downstream product, makes
Its purposes is restricted.
Patent CN103483179 B discloses the purification process of a kind of crude sodium formate byproduct from neopentyl glycol production, and its step is such as
Under: the neopentyl glycol after (1) second distillation produces residue water dissolution, obtains thick sodium formate solution；(2) calcium formate is added,
Precipitation removes oxalate therein and carbonate；(3) add dicyandiamide formaldehyde decolorization flocculation agent and polyacrylamide flocculant, stir
Mix, after placing a period of time, filter or centrifugal；(4) solution after filtering, through being evaporated under reduced pressure, crystallize, being centrifuged, obtains high-purity
Degree sodium formate product.But neopentyl glycol is not reclaimed in this invention.
Patent CN 103483178 A discloses the method processing waste residue in production of neopentyl glycol, the steps include: that (1) is new
Pentanediol produces waste residue water dissolution and obtains thick sodium formate solution；(2) thick sodium formate solution is through accurate filter and ultrafiltration apparatus
It is filtered to remove granule foreign；(3) solution after removing granule foreign enters nanofiltration system and carries out nanofiltration separation；Gained nanofiltration is saturating
Crossing liquid and nanofiltration concentrated solution reclaims high-purity sodium formate, the useful solute in waste residue all reclaims, and impurity produces heat as fuel
Energy.Using ultrafiltration, nanofiltration device decolouring remove impurity in the method, condensing crystallizing obtains white sodium formate, the neopentyl glycol in waste residue
Do not reclaim use, as fuel combustion, add cost.
Summary of the invention
The deficiency existed for prior art, it is an object of the invention to provide a kind of discrimination method production byproduct from neopentyl glycol production thick
The process for purification of sodium formate, the method is simple to operate, and the three wastes are few, it is possible to fully reclaim the neopentyl glycol in crude product, gained formic acid
Sodium white color, quality are high, can be again with, greatly reduce neopentyl glycol production cost.
Process for purification of the present invention, by soluble in water for dark brown sodium formate crude product, is first carried out tentatively crude product with cleaner
Remove impurity, then extracts solution with solvent pairs, obtains white, high-purity sodium formate, reclaims in sodium formate crude product simultaneously
Neopentyl glycol, concrete technical scheme is as follows:
A kind of discrimination method produces the process for purification of crude sodium formate byproduct from neopentyl glycol production, and the method comprises the following steps:
(1) by crude product sodium formate water dissolution, adding cleaner and carry out remove impurity, filter after remove impurity, gained filtrate enters in storage tank；
(2) take the liquid in storage tank, carry out counter-current extraction with isobutylaldehyde as extractant, be layered after extraction, gained isobutylaldehyde phase
After reuse to neopentyl glycol produces workshop section or reclaims isobutylaldehyde, rectification obtains highly purified neopentyl glycol, and the detection of gained aqueous phase is therein
Organic impurity content, as organic impurity content≤2wt%, enters the first aqueous phase and receives tank, as organic impurity content ＞ 2wt%
Time, enter the second aqueous phase and receive tank；
(3) the liquid isooctanol that the second aqueous phase receives in tank being carried out counter-current extraction, be layered after extraction, gained aqueous phase enters the
Three aqueous phases receive tank；
(4) the first aqueous phase receives tank and the 3rd aqueous phase receive the liquid in tank and merge, through concentrating under reduced pressure crystallize, centrifugal, be dried,
Obtaining high-purity sodium formate, the mother solution after being centrifuged returns step (1) as crude product sodium formate dissolving water.
In step of the present invention (1), by sodium formate crude product water dissolution, the part organic impurities in sodium formate is with dope shape
State exists in solution.Sodium formate solution first use cleaner carry out preliminary remove impurity.Described cleaner is activated carbon and 12
The mixture of alkyl benzene calcium sulfonate.Activated carbon has the effect of adsorption bleaching, can reduce the color of solution, but when solution is filtered
Because the existence of activated carbon is filtered very slow, and activated carbon cannot adsorb thickness organic impurities, and this part organic impurities is easily in mistake
Enter in filtrate during filter.The present invention is using the mixture of activated carbon and calcium dodecyl benzene sulfonate as cleaner, dodecane
The addition of base benzenesulfonic acid calcium can increase the rate of filtration of solution when filtering, and plays the effect of drainage, substantially increases filtration
Efficiency, and calcium dodecyl benzene sulfonate can also intercept thickness organic impurities and enter filtrate, improves the removal efficiency of impurity and goes
Except rate.After adding cleaner, solution colour substantially shoals, and is filtered to remove cleaner and thick substances, and gained filtrate is for follow-up
Processing, filtrate is stored in storage tank to take at any time.
In the detailed description of the invention of the present invention, crude product sodium formate, activated carbon, the mass ratio of calcium dodecyl benzene sulfonate are
100:1-5:0.1-0.5, preferably 100:2-4:0.2-0.4.The mass ratio of sodium formate and water is 100:80-200, from saving into
This consideration, preferably 100:80-125.
In the detailed description of the invention of the present invention, in step (1), solution temperature during remove impurity, is kept to be 30-100 DEG C, preferably
For 40-80 DEG C.General, after adding cleaner, stir remove impurity 2-3h.
After remove impurity, the liquid in storage tank being carried out double solvent extraction, double solvent extraction both can reclaim neopentyl glycol, again may be used
With abundant remove impurity.Described solvent pairs is isobutylaldehyde and isooctanol, it is contemplated that isobutylaldehyde is than the isooctanol extraction yield to neopentyl glycol
Higher, the most first reclaim neopentyl glycol with isobutylaldehyde, then with isooctanol, the organic impurities in solution is carried out secondary remove impurity, protect
The quality of card sodium formate.In step (2), during counter-current extraction, the liquid in storage tank is converted into the quality of thick sodium formate and isobutylaldehyde
Ratio is 1:1-1.5, preferably 1:1.1-1.3, and extraction can be carried out in countercurrent extraction equipment, and temperature during isobutylaldehyde extraction is
30-150 DEG C, preferably 50-100 DEG C.There is certain pressure during extraction, extracting pressure is produced by extraction temperature.Because isobutylaldehyde is
The raw material of synthesis neopentyl glycol, therefore extracts the isobutylaldehyde of gained without rectification direct reuse to neopentyl glycol synthesizing section,
It is effectively increased synthesis yield, or repeatedly counter-current extraction can also be carried out with isobutylaldehyde relative to the liquid in storage tank, treat isobutyl
Aldehyde middle neopentyl glycol content mutually reclaims isobutylaldehyde time higher, and rectification obtains neopentyl glycol, it also avoid the waste of neopentyl glycol, improves
Yield.
Further, after isobutylaldehyde counter-current extraction, almost without neopentyl glycol in aqueous phase, go the removal of impurity through cleaner
Content also reduces.According to the content of impurity, aqueous phase carrying out different process, impurity content uses gas chromatographic detection.Work as water
During mutually middle organic impurity content≤2wt%, aqueous phase is entered first aqueous phase receive tank, can directly through concentrating under reduced pressure crystallize, from
The heart, dried, obtain high-purity sodium formate, in order to avoid the discharge of waste water, centrifugal after mother solution return step (1), as crude product
Sodium formate dissolving water；If organic impurity content ＞ 2wt% after cleaner remove impurity, aqueous phase is entered the second aqueous phase and connects by that
Closed cans, to treat to process further.
The liquid isooctanol that second aqueous phase receives in tank carries out counter-current extraction, to remove organic impurities further.Second
It is 1:1-1.5, preferably 1:1.1-1.3 that liquid in aqueous phase reception tank is converted into the mass ratio of thick sodium formate and isooctanol.Extraction
Rear layering, after this extracts, in aqueous phase, organic impurities and the pigment of high molecular are removed further, are entered by gained aqueous phase
3rd aqueous phase receives tank, can obtain, directly through concentrating under reduced pressure crystallize, centrifugal, after drying, the white formic acid that purity is about 99%
Sodium, the centrifuge mother liquor after crystallize also returns to step (1), as crude product sodium formate dissolving water.The such purification operations of the present invention,
Greatly reduce the discharge of the three wastes.
Isooctanol extraction can be carried out in countercurrent extraction equipment, and temperature during isooctanol extraction is 30-150 DEG C, preferably
50-100℃.There is certain pressure during extraction, extracting pressure is produced by extraction temperature.
Further, gained isooctanol as extractant recycled in step (3), when isooctanol mutually in organic miscellaneous
During matter content >=10wt%, stopping applying mechanically, by isooctanol phase air-distillation, the isooctanol of recovery continues as extractant circulating sleeve
With, the residue of distillation can directly mix coal burning disposal.
Further, equipment used when step (2) and (3) counter-current extraction can use in prior art the most permissible
For the equipment of liquid liquid counter-current extraction, counter-current extraction operating process can also be with reference to relevant report of the prior art.
Further, the inventive method can realize industrialization and produce continuously, efficiently, fast, specifically comprises the following steps that
(1) crude product sodium formate and water are mixed in dissolution kettle, be subsequently adding cleaner and carry out remove impurity, filter after remove impurity, gained
Filtrate enters in storage tank；
(2) liquid in storage tank and isobutylaldehyde are pumped into the first countercurrent extraction equipment respectively and carry out counter-current extraction, from the first adverse current
The liquid that extraction equipment flows out enters first layer equipment and is layered, and gained isobutylaldehyde phase reuse produces workshop section to neopentyl glycol
Or rectification obtains highly purified neopentyl glycol after recovery isobutylaldehyde, gained aqueous phase detects organic impurity content therein, when organic miscellaneous
During matter content≤2wt%, enter the first aqueous phase and receive tank, as organic impurity content ＞ 2wt%, enter the second aqueous phase and receive tank；
(3) the second aqueous phase is received the liquid in tank and isooctanol pumps into the second countercurrent extraction equipment respectively and carries out counter-current extraction,
Entering the second layered device from the liquid of the second countercurrent extraction equipment outflow to be layered, gained aqueous phase enters the 3rd aqueous phase and receives
Tank, gained isooctanol is as extractant recycled in step (3), as isooctanol middle organic impurity content >=10wt% mutually
Time, stop applying mechanically, by isooctanol phase air-distillation, the isooctanol of recovery continues to use as extractant, and the residue of distillation is mixed
Coal burning disposal；
(4) the first aqueous phase receives tank and the 3rd aqueous phase receive the liquid in tank and merge, through concentrating under reduced pressure crystallize, centrifugal, be dried,
Obtaining high-purity sodium formate, the mother solution after being centrifuged returns in the storage tank of step (1).
The thick sodium formate of by-product produced when the present invention produces neopentyl glycol to discrimination method provides process for purification, and the method will
Slightly sodium formate dissolves, and first processes with activated carbon and calcium dodecyl benzene sulfonate, playing the effect of the double remove impurity drainage of decolouring, then using
Isobutylaldehyde-isooctanol solvent pairs extracts, and the solution after two step extractions concentrates relieve the effect of alcohol i.e. available white, high concentration first
Acid sodium.The inventive method activated carbon, calcium dodecyl benzene sulfonate, isooctanol carry out twice remove impurity, reclaim new penta with isobutylaldehyde
Glycol.The inventive method is simple to operate, takes a short time, and removal of impurity is high, the recovery to the neopentyl glycol in thick sodium formate
Rate up to more than 98%, refined after sodium formate purity up to the equal reuse of mother solution in more than 99%, and subtractive process and extraction phase, three
Useless discharge less, environmental pollution little, it is achieved that the effective recycling of resource, there is good practical value.
Detailed description of the invention
Below by embodiment, the present invention is further elaborated, it should be appreciated that, the description below is only used to
Explain the present invention, its content is not limited.
Embodiment 1
1, at 10m3Adding 5000kg water in dissolution kettle, stirring adds 5000kg sodium formate crude product (sodium formate content 88%, moisture
6%, neopentyl glycol content 4%, other organic impuritiess 2%), it is heated to 50 DEG C of dissolvings, adds 100kg activated carbon and 5kg dodecyl
Benzenesulfonic acid calcium, keeps 50 DEG C of remove impurity 2h.Insulation afterwards is filtered to remove activated carbon and thick substances, and filtration required time is 15min,
Filtrate enters storage tank and stores.
2, metering isobutylaldehyde, according to the mass ratio of the sodium formate in storage tank filtrate Yu isobutylaldehyde be 1:1.1 use magnitude relation
Filtrate and isobutylaldehyde transport pump to airtight counter current contacting continuous extraction tower are carried out counter-current extraction, and extraction temperature is 80 DEG C, from
The liquid that extraction tower flows out flows into layering tower and is layered, and layering tower pressure is 0.2MPa, and isobutylaldehyde flows out from upper strata, amounts to
Weight is 6080.5kg, and gas chromatogram fixative is analyzed wherein neopentyl glycol content and is 3.23% (the equivalent neopentyl glycol response rate is
98.2%) can enter neopentyl glycol synthesis reactor as neopentyl glycol synthesis material, aqueous phase flows out from layering tower bottom.
3, in GC-External Standard method determination step 2 aqueous phase, high boiling point organic impurity content is 0.85%, less than 2%, and should
Aqueous phase stores to the first aqueous phase reception tank.Then the first aqueous phase is received after the liquid pressure-reducing in tank is concentrated into precipitation crystallization and lower the temperature
Centrifugal, filter cake obtains white sodium formate after drying, its purity of chemical analysis is 99.2%, and the mother solution after being centrifuged returns step (1),
Dissolve sodium formate crude product water as lower batch to use.
According to aforesaid operations serialization, sodium formate crude product is refined, after centrifuge mother liquor applies mechanically 15 times, step 2 is divided
In the aqueous phase of layer gained, high boiling point organic impurity content becomes 2.1%, this aqueous phase enters the second aqueous phase reception tank and stores.
Metering isooctanol, is being received by the second aqueous phase with magnitude relation of 1:1.1 according to the mass ratio of the sodium formate in liquid Yu isooctanol
Liquid in tank carries out counter-current extraction with isooctanol transport pump to airtight counter current continuous extraction tower, and extraction temperature is 80 DEG C, from
The liquid that extraction tower flows out flows into layering tower, and lower floor is aqueous phase, is stored by this aqueous phase to the 3rd aqueous phase and receives tank, after testing this
It is 0.9% that three aqueous phases receive high boiling point organic impurity content in the liquid in tank, less than 2%, the 3rd aqueous phase is received the liquid in tank
Body is incorporated to the first aqueous phase and receives tank and enter sodium formate condensing crystallizing workshop section, obtains white sodium formate.Flow out from layering tower upper strata
Being isooctanol phase, upper strata isooctanol is circulated mutually and applies mechanically, and continues to receive the new liq in tank with the second aqueous phase and carries out countercurrently extracting
Taking, when middle high boiling point organic impurities cumulative amount reaches 10% to isooctanol mutually, enter isooctanol distillation column, air-distillation is reclaimed
Isooctanol, bottom is mixed coal and is burned.
According to aforesaid operations, repeat to apply mechanically 15 times, total input 75000kg sodium formate crude product, obtain sodium formate fine work
62700kg, its purity of chemical analysis is 99.2%, and the refined yield of sodium formate is 94.2%.Isobutylaldehyde fully recovering after extraction
To neopentyl glycol synthesizing section, the many 2950kg of neopentyl glycol product population, the equivalent neopentyl glycol response rate is 98.3%.
Embodiment 2
1, at 10m3Dissolution kettle adds 5m3Water, stirring addition 2500kg sodium formate crude product (sodium formate content 88%, moisture 6%,
Neopentyl glycol content 4%, other organic impuritiess 2%), it is heated to 40 DEG C of dissolvings, adds 75kg activated carbon and 5kg detergent alkylate sulphur
Acid calcium, keeps 30 DEG C of remove impurity 2h.Insulation afterwards is filtered to remove activated carbon and thick substances, and filtration required time is 12min, filtrate
Entrance storage tank stores.
2, metering isobutylaldehyde, according to the mass ratio of the sodium formate in storage tank filtrate Yu isobutylaldehyde be 1:1.3 use magnitude relation
Filtrate and isobutylaldehyde transport pump to airtight counter current contacting continuous extraction tower are carried out counter-current extraction, and extraction temperature is 110 DEG C, from
The liquid that extraction tower flows out flows into layering tower and is layered, and layering tower pressure is 0.4MPa, and isobutylaldehyde flows out from upper strata, isobutyl
Aldehyde phase weight is 3740kg, and it is 2.72% (the equivalent neopentyl glycol response rate that gas chromatogram fixative analyzes wherein neopentyl glycol content
It is 98.3%) neopentyl glycol synthesis reactor can be entered as neopentyl glycol synthesis material, aqueous phase flows out from layering tower bottom.
3, in GC-External Standard method determination step 2 aqueous phase, high boiling point organic impurity content is 0.75%, stores to the first water
Connect closed cans.Then the first aqueous phase is received cooling after the liquid pressure-reducing in tank is concentrated into precipitation crystallization centrifugal, after filter cake is dried
Obtaining white sodium formate, its purity of chemical analysis is 99.2%, and the mother solution after being centrifuged returns step (1), dissolves formic acid as lower batch
Sodium crude product water uses.
After centrifuge mother liquor applies mechanically 15 times, in step 2, in aqueous phase, high boiling point organic impurity content is 2.08%, by this aqueous phase
Enter the second aqueous phase reception tank to store.Metering isooctanol, is 1 according to the mass ratio of the sodium formate in liquid Yu isooctanol:
1.3 the liquid in the second aqueous phase reception tank is carried out with isooctanol transport pump to airtight counter current continuous extraction tower with magnitude relation
Counter-current extraction, extraction temperature is 100 DEG C, and the liquid flowed out from extraction tower flows into layering tower, and lower floor is aqueous phase, is stored by this aqueous phase
Receiving tank to the 3rd aqueous phase, during the 3rd aqueous phase receives the liquid in tank after testing, high boiling point organic impurity content is 0.88%, by the
Three aqueous phases receive the liquid in tanks and are incorporated to the first aqueous phase and receive tank and enter sodium formate condensing crystallizing workshop section, obtain white sodium formate.
Flow out from layering tower upper strata for isooctanol phase, upper strata isooctanol phase recycled, that continues with the second aqueous phase reception tank is new
Liquid carries out counter-current extraction, when middle high boiling point organic impurities cumulative amount reaches 10% to isooctanol mutually, enters isooctanol distillation
Tower, air-distillation recovery isooctanol, bottom is mixed coal and is burned.
According to aforesaid operations, repeat to apply mechanically 15 times, total input 37500kg sodium formate crude product, obtain sodium formate fine work
31300kg, its purity of chemical analysis is 99.2%, and the refined yield of sodium formate is 94.1%.Isobutylaldehyde fully recovering after extraction
To neopentyl glycol synthesizing section, neopentyl glycol product population has more 1471.5kg, and the equivalent neopentyl glycol response rate is 98.1%.
Embodiment 3
1, at 10m3Dissolution kettle adds 5m3Water, stirring addition 4000kg sodium formate crude product (sodium formate content 88%, moisture 6%,
Neopentyl glycol content 4%, other organic impuritiess 2%), it is heated to 100 DEG C of dissolvings, adds 200kg activated carbon and 20kg dodecyl
Benzenesulfonic acid calcium, keeps 100 DEG C of remove impurity 2h.Insulation afterwards is filtered to remove activated carbon and thick substances, filters required time and is
12min, filtrate enters storage tank and stores.
2, metering isobutylaldehyde, according to the mass ratio of the sodium formate in storage tank filtrate Yu isobutylaldehyde be 1:1.5 use magnitude relation
Filtrate and isobutylaldehyde transport pump to airtight counter current contacting continuous extraction tower are carried out counter-current extraction, and extraction temperature is 50 DEG C, from
The liquid that extraction tower flows out flows into layering tower and is layered, and layering tower pressure is 0.025MPa, and isobutylaldehyde flows out from upper strata, claims
Being heavily 5275kg, gas chromatogram fixative is analyzed wherein neopentyl glycol content and is 3.12% (the equivalent neopentyl glycol response rate is
97.0%) can enter neopentyl glycol synthesis reactor as neopentyl glycol synthesis material, aqueous phase flows out from layering tower bottom.
3, in GC-External Standard method determination step 2 aqueous phase, high boiling point organic impurity content is 0.95%, stores to the first water
Connect closed cans.Then the first aqueous phase is received cooling after the liquid pressure-reducing in tank is concentrated into precipitation crystallization centrifugal, after filter cake is dried
Obtaining white sodium formate, its purity of chemical analysis is 99.2%, and the mother solution after being centrifuged returns step (1), dissolves formic acid as lower batch
Sodium crude product water uses.
After centrifuge mother liquor applies mechanically 15 times, in step 2, in aqueous phase, high boiling point organic impurity content is 2.28%, by this aqueous phase
Enter the second aqueous phase reception tank to store.Metering isooctanol, is 1 according to the mass ratio of the sodium formate in liquid Yu isooctanol:
1.5 the liquid in the second aqueous phase reception tank is carried out with isooctanol transport pump to airtight counter current continuous extraction tower with magnitude relation
Counter-current extraction, extraction temperature is 100 DEG C, and the liquid flowed out from extraction tower flows into layering tower, and lower floor is aqueous phase, is stored by this aqueous phase
Receiving tank to the 3rd aqueous phase, during the 3rd aqueous phase receives the liquid in tank after testing, high boiling point organic impurity content is 0.91%, by the
Three aqueous phases receive the liquid in tanks and are incorporated to the first aqueous phase and receive tank and enter sodium formate condensing crystallizing workshop section, obtain white sodium formate.
Flow out from layering tower upper strata for isooctanol phase, upper strata isooctanol phase recycled, that continues with the second aqueous phase reception tank is new
Liquid carries out counter-current extraction, when middle high boiling point organic impurities cumulative amount reaches 10% to isooctanol mutually, enters isooctanol distillation
Tower, air-distillation recovery isooctanol, bottom is mixed coal and is burned.
According to aforesaid operations, repeat to apply mechanically 15 times, total input 60000kg sodium formate crude product, obtain sodium formate fine work
49800kg, its purity of chemical analysis is 99.2%, and the refined yield of sodium formate is 93.6%.Isobutylaldehyde fully recovering after extraction
To neopentyl glycol synthesizing section, neopentyl glycol product population has more 2328kg, and the equivalent neopentyl glycol response rate is 97.0%.
Embodiment 4
1, at 10m3Dissolution kettle adds 5m3Water, stirring addition 6250kg sodium formate crude product (sodium formate content 88%, moisture 6%,
Neopentyl glycol content 4%, other organic impuritiess 2%), it is heated to 80 DEG C of dissolvings, adds 312.5kg activated carbon and 30kg dodecyl
Benzenesulfonic acid calcium, keeps 80 DEG C of remove impurity 3h.Insulation afterwards is filtered to remove activated carbon and thick substances, and filtration required time is 12min,
Filtrate enters storage tank and stores.
2, metering isobutylaldehyde, according to the mass ratio of the sodium formate in storage tank filtrate Yu isobutylaldehyde be 1:1.1 use magnitude relation
Filtrate and isobutylaldehyde transport pump to airtight counter current contacting continuous extraction tower are carried out counter-current extraction, and extraction temperature is 80 DEG C, from
The liquid that extraction tower flows out flows into layering tower and is layered, and layering tower pressure is 0.2MPa, and isobutylaldehyde flows out from upper strata, gross weight
For 9760kg, it is 2.61% (the equivalent neopentyl glycol response rate is 98.2%) that gas chromatogram fixative analyzes wherein neopentyl glycol content
Can enter neopentyl glycol synthesis reactor as neopentyl glycol synthesis material, aqueous phase flows out from layering tower bottom.
3, in GC-External Standard method determination step 2 aqueous phase, high boiling point organic impurity content is 1.25%, stores to the first water
Connect closed cans.Then the first aqueous phase is received cooling after the liquid pressure-reducing in tank is concentrated into precipitation crystallization centrifugal, after filter cake is dried
Obtaining white sodium formate, its purity of chemical analysis is 99.1%, and the mother solution after being centrifuged returns step (1), dissolves formic acid as lower batch
Sodium crude product water uses.
After centrifuge mother liquor applies mechanically 15 times, in step 2, in aqueous phase, high boiling point organic impurity content is 2.13%, by this aqueous phase
Enter the second aqueous phase reception tank to store.Metering isooctanol, is 1 according to the mass ratio of the sodium formate in liquid Yu isooctanol:
1.1 the liquid in the second aqueous phase reception tank is carried out with isooctanol transport pump to airtight counter current continuous extraction tower with magnitude relation
Counter-current extraction, extraction temperature is 150 DEG C, and the liquid flowed out from extraction tower flows into layering tower, and lower floor is aqueous phase, is stored by this aqueous phase
Receiving tank to the 3rd aqueous phase, during the 3rd aqueous phase receives the liquid in tank after testing, high boiling point organic impurity content is 0.98%, by the
Three aqueous phases receive the liquid in tanks and are incorporated to the first aqueous phase and receive tank and enter sodium formate condensing crystallizing workshop section, obtain white sodium formate.
Flow out from layering tower upper strata for isooctanol phase, upper strata isooctanol phase recycled, that continues with the second aqueous phase reception tank is new
Liquid carries out counter-current extraction, when middle high boiling point organic impurities cumulative amount reaches 10% to isooctanol mutually, enters isooctanol distillation
Tower, air-distillation recovery isooctanol, bottom is mixed coal and is burned.
According to aforesaid operations, repeat to apply mechanically 15 times, total input 93750kg sodium formate crude product, obtain sodium formate fine work
78254kg, its purity of chemical analysis is 99.1%, and the refined yield of sodium formate is 94.0%.Isobutylaldehyde fully recovering after extraction
To neopentyl glycol synthesizing section, neopentyl glycol product population has more 3675kg, and the equivalent neopentyl glycol response rate is 98.0%.
Embodiment 5
1, at 10m3Dissolution kettle adds 5m3Water, stirring addition 2500kg sodium formate crude product (sodium formate content 88%, moisture 6%,
Neopentyl glycol content 4%, other organic impuritiess 2%), it is heated to 30 DEG C of dissolvings, adds 25kg activated carbon and 2.5kg detergent alkylate
Sulfoacid calcium, keeps 30 DEG C of remove impurity 3h.Insulation afterwards is filtered to remove activated carbon and thick substances, and filtration required time is 15min, filter
Liquid enters storage tank and stores.
2, metering isobutylaldehyde, according to the mass ratio of the sodium formate in storage tank filtrate Yu isobutylaldehyde be 1:1.5 use magnitude relation
Filtrate and isobutylaldehyde transport pump to airtight counter current contacting continuous extraction tower are carried out counter-current extraction, and extraction temperature is 30 DEG C, from
The liquid that extraction tower flows out flows into layering tower and is layered, and isobutylaldehyde flows out from upper strata, and gas chromatogram fixative is analyzed wherein
Neopentyl glycol content is 2.50%, can enter neopentyl glycol synthesis reactor as neopentyl glycol synthesis material, and aqueous phase is from layering tower bottom
Flow out.
3, in GC-External Standard method determination step 2 aqueous phase, high boiling point organic impurity content is 1.48%, stores to the first water
Connect closed cans.Then the first aqueous phase is received cooling after the liquid pressure-reducing in tank is concentrated into precipitation crystallization centrifugal, after filter cake is dried
Obtaining white sodium formate, its purity of chemical analysis is 99.0%, and the mother solution after being centrifuged returns step (1), dissolves formic acid as lower batch
Sodium crude product water uses.
After centrifuge mother liquor applies mechanically 14 times, in step 2, in aqueous phase, high boiling point organic impurity content is 2.15%, by this aqueous phase
Enter the second aqueous phase reception tank to store.Metering isooctanol, is 1 according to the mass ratio of the sodium formate in liquid Yu isooctanol:
1.5 the liquid in the second aqueous phase reception tank is carried out with isooctanol transport pump to airtight counter current continuous extraction tower with magnitude relation
Counter-current extraction, extraction temperature is 30 DEG C, and the liquid flowed out from extraction tower flows into layering tower, and lower floor is aqueous phase, is stored by this aqueous phase
Receiving tank to the 3rd aqueous phase, during the 3rd aqueous phase receives the liquid in tank after testing, high boiling point organic impurity content is 1.11%, by the
Three aqueous phases receive the liquid in tanks and are incorporated to the first aqueous phase and receive tank and enter sodium formate condensing crystallizing workshop section, obtain white sodium formate.
Flow out from layering tower upper strata for isooctanol phase, upper strata isooctanol phase recycled, that continues with the second aqueous phase reception tank is new
Liquid carries out counter-current extraction, when middle high boiling point organic impurities cumulative amount reaches 10% to isooctanol mutually, enters isooctanol distillation
Tower, air-distillation recovery isooctanol, bottom is mixed coal and is burned.
According to aforesaid operations, repeat to apply mechanically 14 times, total input 35000kg sodium formate crude product, obtain sodium formate fine work
33232.3kg, its purity of chemical analysis is 99.0%, and the refined yield of sodium formate is 94.0%.Isobutylaldehyde after extraction all returns
With to neopentyl glycol synthesizing section, neopentyl glycol product population has more 1372kg, and the equivalent neopentyl glycol response rate is 98.0%.
Comparative example 1
1, at 10m3Adding 5000kg water in dissolution kettle, stirring adds 5000kg sodium formate crude product (sodium formate content 88%, moisture
6%, neopentyl glycol content 4%, other organic impuritiess 2%), it is heated to 50 DEG C of dissolvings, adds 100kg activated carbon, keep 50 DEG C of remove impurity
2h.Insulation afterwards is filtered to remove activated carbon and thick substances, and filtration required time is 2h, and filtrate enters storage tank and stores.
2, metering isobutylaldehyde, according to the mass ratio of the sodium formate in storage tank filtrate Yu isobutylaldehyde be 1:1.1 use magnitude relation
Filtrate and isobutylaldehyde transport pump to airtight counter current contacting continuous extraction tower are carried out counter-current extraction, and extraction temperature is 80 DEG C, from
The liquid that extraction tower flows out flows into layering tower and is layered, and layering tower pressure is 0.2MPa, and isobutylaldehyde flows out from upper strata, amounts to
Weight is 6075kg, and gas chromatogram fixative is analyzed wherein neopentyl glycol content and is 3.22% (the equivalent neopentyl glycol response rate is
97.9%) can enter neopentyl glycol synthesis reactor as neopentyl glycol synthesis material, aqueous phase flows out from layering tower bottom.
3, in GC-External Standard method determination step 2 aqueous phase, high boiling point organic impurity content is 0.87%, less than 2%, and should
Aqueous phase stores to the first aqueous phase reception tank.Then the first aqueous phase is received after the liquid pressure-reducing in tank is concentrated into precipitation crystallization and lower the temperature
Centrifugal, filter cake obtains white sodium formate after drying, its purity of chemical analysis is 99.2%, and the mother solution after being centrifuged returns step (1),
Dissolve sodium formate crude product water as lower batch to use.
According to aforesaid operations serialization, sodium formate crude product is refined, after centrifuge mother liquor applies mechanically 13 times, step 2 is divided
In the aqueous phase of layer gained, high boiling point organic impurity content becomes 2.1%, this aqueous phase enters the second aqueous phase reception tank and stores.
Metering isooctanol, is being received by the second aqueous phase with magnitude relation of 1:1.1 according to the mass ratio of the sodium formate in liquid Yu isooctanol
Liquid in tank carries out counter-current extraction with isooctanol transport pump to airtight counter current continuous extraction tower, and extraction temperature is 80 DEG C, from
The liquid that extraction tower flows out flows into layering tower, and lower floor is aqueous phase, is stored by this aqueous phase to the 3rd aqueous phase and receives tank, after testing this
It is 0.9% that three aqueous phases receive high boiling point organic impurity content in the liquid in tank, less than 2%, the 3rd aqueous phase is received the liquid in tank
Body is incorporated to the first aqueous phase and receives tank and enter sodium formate condensing crystallizing workshop section, obtains white sodium formate.Flow out from layering tower upper strata
Being isooctanol phase, upper strata isooctanol is circulated mutually and applies mechanically, and continues to receive the new liq in tank with the second aqueous phase and carries out countercurrently extracting
Taking, when middle high boiling point organic impurities cumulative amount reaches 10% to isooctanol mutually, enter isooctanol distillation column, air-distillation is reclaimed
Isooctanol, bottom is mixed coal and is burned.
According to aforesaid operations, repeat to apply mechanically 13 times, total input 65000kg sodium formate crude product, obtain sodium formate fine work
54311kg, its purity of chemical analysis is 99.0%, and the refined yield of sodium formate is 94.0%.Isobutylaldehyde fully recovering after extraction
To neopentyl glycol synthesizing section, the many 2545kg of neopentyl glycol product population, the equivalent neopentyl glycol response rate is 97.9%.
Claims (10)
1. discrimination method produces a process for purification for crude sodium formate byproduct from neopentyl glycol production, it is characterized in that comprising the following steps:
(1) by crude product sodium formate water dissolution, adding cleaner and carry out remove impurity, filter after remove impurity, gained filtrate enters in storage tank；
(2) take the liquid in storage tank, carry out counter-current extraction with isobutylaldehyde as extractant, be layered after extraction, gained isobutylaldehyde phase
After reuse to neopentyl glycol produces workshop section or reclaims isobutylaldehyde, rectification obtains highly purified neopentyl glycol, and the detection of gained aqueous phase is therein
Organic impurity content, as organic impurity content≤2wt%, enters the first aqueous phase and receives tank, as organic impurity content ＞ 2wt%
Time, enter the second aqueous phase and receive tank；
(3) the liquid isooctanol that the second aqueous phase receives in tank being carried out counter-current extraction, be layered after extraction, gained aqueous phase enters the
Three aqueous phases receive tank；
(4) the first aqueous phase receives tank and the 3rd aqueous phase receive the liquid in tank and merge, through concentrating under reduced pressure crystallize, centrifugal, be dried,
Obtaining high-purity sodium formate, the mother solution after being centrifuged returns step (1) as crude product sodium formate dissolving water.
Process for purification the most according to claim 1, is characterized in that: in step (3), and layering gained isooctanol is mutually as extraction
Taking agent recycled in step (3), as isooctanol middle organic impurity content >=10wt% mutually, stopping is applied mechanically, air-distillation,
The isooctanol reclaimed continues to use as extractant, and the residue of distillation mixes coal burning disposal.
Process for purification the most according to claim 1, is characterized in that: described cleaner is activated carbon and detergent alkylate sulphur
The mixture of acid calcium.
Process for purification the most according to claim 3, is characterized in that: crude product sodium formate, activated carbon, DBSA
The mass ratio of calcium is 100:1-5:0.1-0.5, preferably 100:2-4:0.2-0.4.
Process for purification the most according to claim 1, is characterized in that: the mass ratio of crude product sodium formate and water is 100:80-
200, preferably 100:80-125.
Process for purification the most according to claim 1, is characterized in that: in step (1), and during remove impurity, holding solution temperature is
30-100 DEG C, preferably 40-80 DEG C.
Process for purification the most according to claim 1, is characterized in that: in step (1), after adding cleaner, stirs remove impurity
2-3h。
Process for purification the most according to claim 1, is characterized in that: in step (2), liquid during counter-current extraction, in storage tank
It is 1:1-1.5, preferably 1:1.1-1.3 that body is converted into the mass ratio of thick sodium formate and isobutylaldehyde；In step (3), during counter-current extraction,
It is 1:1-1.5, preferably 1:1.1-1.3 that liquid in second aqueous phase reception tank is converted into the mass ratio of thick sodium formate and isooctanol.
Process for purification the most according to claim 1, is characterized in that: in step (2) and (3), the temperature of counter-current extraction is equal
For 30-150 DEG C, preferably 50-100 DEG C.
Process for purification the most according to claim 1, is characterized in that: include step in detail below:
(1) crude product sodium formate and water are mixed in dissolution kettle, be subsequently adding cleaner and carry out remove impurity, filter after remove impurity, gained
Filtrate enters in storage tank；
(2) liquid in storage tank and isobutylaldehyde are pumped into the first countercurrent extraction equipment respectively and carry out counter-current extraction, from the first adverse current
The liquid that extraction equipment flows out enters first layer equipment and is layered, and gained isobutylaldehyde phase reuse produces workshop section to neopentyl glycol
Or rectification obtains highly purified neopentyl glycol after recovery isobutylaldehyde, gained aqueous phase detects organic impurity content therein, when organic miscellaneous
During matter content≤2wt%, enter the first aqueous phase and receive tank, as organic impurity content ＞ 2wt%, enter the second aqueous phase and receive tank；
(3) the second aqueous phase is received the liquid in tank and isooctanol pumps into the second countercurrent extraction equipment respectively and carries out counter-current extraction,
Entering the second layered device from the liquid of the second countercurrent extraction equipment outflow to be layered, gained aqueous phase enters the 3rd aqueous phase and receives
Tank, gained isooctanol is as extractant recycled in step (3), as isooctanol middle organic impurity content >=10wt% mutually
Time, stop applying mechanically, by isooctanol phase air-distillation, the isooctanol of recovery continues to use as extractant, and the residue of distillation is mixed
Coal burning disposal；
(4) the first aqueous phase receives tank and the 3rd aqueous phase receive the liquid in tank and merge, through concentrating under reduced pressure crystallize, centrifugal, be dried,
Obtaining high-purity sodium formate, the mother solution after being centrifuged returns step (1) as crude product sodium formate dissolving water.
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