CN100363327C - Production of pivalic acid - Google Patents
Production of pivalic acid Download PDFInfo
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- CN100363327C CN100363327C CNB2005100037986A CN200510003798A CN100363327C CN 100363327 C CN100363327 C CN 100363327C CN B2005100037986 A CNB2005100037986 A CN B2005100037986A CN 200510003798 A CN200510003798 A CN 200510003798A CN 100363327 C CN100363327 C CN 100363327C
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Abstract
The present invention relates to a method for preparing pivalic acid. C4 fraction which does not contain butadiene, sulfuric acid and carbon monoxide are used as raw materials. C4 fraction which does not contain butadiene and the sulfuric acid are mixed in a reactor, and are esterified at certain temperature and pressure. Raffinate containing little isobutylene on the upper layer is removed, and the lower layer and the carbon monoxide are carbonylated, and are prepared into the finished product after being hydrolyzed and separated. The present invention is characterized in that the C4 fraction (1) which does not contain butadiene is used for replacing the isobutylene, and thus, pivalic acid is prepared. Compared with the prior art, the C4 fraction (1) which does not contain butadiene, the sulfuric acid and the carbon monoxide react to prepare the pivalic acid. One part of the diluted sulfuric acid is directly used as raw material for esterification reaction after the hydrolysis reaction, and the other part of the diluted sulfuric acid is used as raw material of carbonylation reaction to be recycled after being concentrated. Compared with the process for preparing the isobutylene to be carbonylated into the pivalic acid by a sulfuric acid absorption-decomposition method, the present invention reduces the procedures of the hydrolyzation of the sulfuric acid tert-butyl ester, the dehydration of the tertiary butyl alcohol and the rectification of the crude isobutylene, the concentration quantity of the diluted sulfuric acid, and the investment, and decreases the energy consumption, and thus, the production cost is greatly reduced.
Description
Technical field
The invention belongs to a kind of production method of Chemicals, especially relate to a kind of method that adopts synthetic method to produce trimethylacetic acid.
Background technology
Trimethylacetic acid claims trimethylacetic acid or 2 again, and the 2-neopentanoic acid is English by name: pivalic acid (being called for short PA), and CA registration number: 75-98-9, molecular formula is: C
5H
10O
2, structural formula is:
Molecular weight is 102.13, and normal temperature for white solid, has special odor down, and fusing point is 35.5 ℃, and boiling point is 163～164 ℃, and density is 0.905g/cm
3, flash-point is 63 ℃, is slightly soluble in water, is soluble in alcohol, ether, has certain corrodibility.Should be placed on lucifuge shady and cool local and inflated with nitrogen protection or vacuum-sealing storage, deepen to prevent product colour.As a kind of important chemical material and chemical reagent, be mainly used in synthetic polymer initiator, pesticide intermediate, medicine intermediate, softening agent, foodstuff additive, coating, lubricating oil, Racemic glycidol, dispersion agent, spices etc., in fine chemical product is synthetic, also be widely used.
Before the present invention made, the method for synthetic trimethylacetic acid mainly contained five kinds in the prior art: special valeral or tert-pentanol method, trimethyl carbinol method, isopropylcarbinol method, iso-butylene method, isopropanol method.Wherein the iso-butylene method is the domestic and international at present generally method of the suitability for industrialized production trimethylacetic acid of employing.
The process of prior art for preparing trimethylacetic acid is earlier with sulfuric acid absorption---decomposition method or methyl tertiary butyl ether method never contain that separation and purification gets iso-butylene in the C-4-fraction of divinyl, then iso-butylene and sulfuric acid are mixed back and reaction of carbon monoxide.Below with sulfuric acid absorption---decomposition method and methyl tertiary butyl ether method preparing isobutene and iso-butylene legal system trimethylacetic acid are that example is launched explanation.
One, the preparation of iso-butylene
1, sulfuric acid absorption---decomposition method preparing isobutene
This method has more application abroad, and domestic basic not employing.Existing sulfuric acid absorption--during-decomposition method preparing isobutene, the C-4-fraction and the sulfuric acid that will not contain divinyl earlier mix, make iso-butylene and 50% sulfuric acid reaction in the C-4-fraction that does not contain divinyl generate the sulfuric acid tert-butyl ester, the hydrolysis of the sulfuric acid tert-butyl ester gets the trimethyl carbinol and sulfuric acid then, sulfuric acid is carried and being recycled after dense, trimethyl carbinol dehydration obtains iso-butylene, makes purity reach (idiographic flow is seen accompanying drawing 1) more than 99% after purifying.Its reaction process is as follows:
2, methyl tertiary butyl ether cracking process
This method is the domestic method of generally using.With the C-4-fraction and the methyl alcohol that do not contain divinyl is raw material, generate methyl tertiary butyl ether at synthetic reaction device, obtain iso-butylene and methyl alcohol in the cracking reactor cracking then, separate through knockout tower, the top is thick iso-butylene, and the bottom is methyl alcohol and the uncracked methyl tertiary butyl ether that scission reaction obtains, and bottom product is recycled to synthesizer, thick iso-butylene gets the product iso-butylene behind eparating methanol tower and iso-butylene purification tower, methanol loop is used (idiographic flow is seen accompanying drawing 2).Its reaction formula is as follows:
Two, iso-butylene legal system trimethylacetic acid technology
With the iso-butylene more than 99% is raw material, iso-butylene is dissolved in the solvent (as trichloromethane), exist the logical carbon monoxide of downhill reaction device to reach 5Mpa at sulfuric acid to the still internal pressure, stir half an hour under the room temperature after hydrolysis, drying and distillation make trimethylacetic acid, reaction yield reaches 74%, and product purity reaches 99% (idiographic flow is seen accompanying drawing 3).Its reaction process is as follows:
This method is that raw material reaction is produced trimethylacetic acid with iso-butylene, sulfuric acid and carbon monoxide.But, owing to be raw material with pure iso-butylene, and pure iso-butylene is made by sulfuric acid absorption-decomposition method or methyl tertiary butyl ether cracking process this method, the cost height in actual production, make the trimethylacetic acid cost of producing higher, thereby influenced this type of competition capability.
Summary of the invention
For overcome prior art on deficiency, the invention provides a kind of method of new production trimethylacetic acid, utilize this method to produce trimethylacetic acid and have technical process and simply reach the low advantage of production cost.
For achieving the above object, the present invention has taked following technical scheme: this method is not to contain the C-4-fraction of divinyl, sulfuric acid and carbon monoxide are raw material, earlier C-4-fraction that does not contain divinyl and sulfuric acid are mixed, under certain temperature and pressure, carry out esterification, dividing goes to the upper strata to contain the raffinate that iso-butylene seldom (promptly is substantially devoid of iso-butylene), lower floor mainly is the sulfuric acid tert-butyl ester and a spot of trimethyl carbinol, after isolating subnatant subnatant and carbon monoxide are carried out carbonylation reaction in the presence of sulfuric acid, reactant is through hydrolysis, make finished product after the separation, its advantage is: substitute iso-butylene with the C-4-fraction that does not contain divinyl and produce trimethylacetic acid, saved the process of producing of complicated iso-butylene, a dilute sulphuric acid part that produces is as the raw material of esterification, and another part is made the oxonation raw material after dense and recycled through carrying.Its reaction expression is:
Among the present invention, except as otherwise noted, term " C-4-fraction that does not contain divinyl " is meant: the raffinate of the C-4-fraction of cracking ethylene preparation device by-product behind the extracting divinyl and the C-4-fraction of catalytic cracking system ethylene unit by-product.Wherein, the content of iso-butylene (mass content) is 10%-50%, is preferably 40%-50%, and surplus is mainly Trimethylmethane, 1-butylene, normal butane, anti-2-butylene, suitable 2-butylene and a spot of 1,3-butadiene.
In the specific implementation, the content (mass content) that does not contain iso-butylene in the C-4-fraction of divinyl is 10%-50%, classical group becomes iso-butylene 45%, Trimethylmethane 3%, 1-butylene 25%, normal butane 11%, anti-2-butylene 9%, suitable 2-butylene 7% and 1,3-butadiene＜0.5%.
Temperature during esterification is 10-90 ℃, and preferred 15-40 ℃, 40-50 ℃ temperature also is preferred, pressure is 0.1-2.0Mpa, preferred 0.12-0.45Mpa, and the temperature during carbonylation reaction is 0-100 ℃, preferred 20-30 ℃, pressure is 1.0-8.0Mpa, preferred 4.5-5.5Mpa, temperature during hydrolysis reaction is 0-100 ℃, preferred 5-15 ℃, pressure is 0-1.0Mpa, preferred 0.1-0.5Mpa, wherein in carbonylation reaction, select H for use
2SO
4As catalyzer.
Beneficial effect: because the present invention adopts the C-4-fraction that does not contain divinyl to replace pure iso-butylene of the prior art and sulfuric acid and reaction of carbon monoxide to produce trimethylacetic acid, dilute sulphuric acid part behind the hydrolysis reaction is directly as the raw material of esterification, and another part recycles as the carbonylation reaction raw material after concentrating.Compare with the process of sulfuric acid absorption one decomposition method preparing isobutene and then carbonylation system trimethylacetic acid, the present invention has reduced the hydrolysis of the sulfuric acid tert-butyl ester, the dehydration of the trimethyl carbinol, the rectification working process of thick iso-butylene, has reduced dilute sulphuric acid and has concentrated amount.Reduce investment and reduced energy consumption, therefore greatly reduced production cost.
Description of drawings
Accompanying drawing 1 is that sulfuric acid absorption-decomposition method is produced the iso-butylene process flow sheet.
Accompanying drawing 2 is produced the iso-butylene process flow sheet for the methyl tertiary butyl ether method.
Accompanying drawing 3 is the process flow sheet of existing explained hereafter trimethylacetic acid.
Accompanying drawing 4 is technological process of production figure of the present invention.
Embodiment
4 the present invention is further described in detail with reference to the accompanying drawings by embodiment.
Example one
With 1.65 tons of C-4-fraction (iso-butylenes 45% that do not contain divinyl, Trimethylmethane 3%, 1-butylene 25%, normal butane 11%, anti-2-butylene 9%, suitable 2-butylene 7% and 1,3-divinyl＜0.5%) and 2.7 ton of 50% sulfuric acid be raw material, temperature of reaction 15-40 ℃ and pressure 0.12-0.45Mpa enter sulfuric acid absorption tower respectively and carry out esterification.Mixture (the sulfuric acid tert-butyl ester of reaction, the trimethyl carbinol and contain iso-butylene amount raffinate seldom) enter separator and separate, lower floor's mixture (sulfuric acid tert-butyl ester, the trimethyl carbinol) enters the flashing tower flash distillation, remove the hydrocarbon compound of trace, the mixture that obtains (total content of the sulfuric acid tert-butyl ester and the trimethyl carbinol reaches more than 99% by analysis), enter mixing tank and mix from the trichloromethane of solvent tank, mixed solution enters carbonylation reactor, in carbonylation reactor, add 4.3 ton of 85% sulfuric acid simultaneously, temperature of reaction 20-30 ℃ and pressure 4.5-5.5Mpa carry out carbonylation reaction, (the sulfuric acid tert-butyl ester carbonylation product of mixture behind the carbonylation reaction, the trimethyl carbinol, trichloromethane, sulfuric acid) enter hydrolysis reactor, and in hydrolysis reactor, add frozen water, temperature of reaction 5-15 ℃ and the pressure 0.1-0.5Mpa reaction that is hydrolyzed, reaction product enters separator, upper strata trichloromethane layer enters light phase storage tank, lower aqueous layer enters the heavy phase storage tank, after enter the extraction tower chloroform extraction, upper strata trichloromethane layer after the extraction gets 1 ton of product with light storage tank mixture mutually after refining, through stratographic analysis is trimethylacetic acid more than 99%, the solvent trichloromethane returns solvent tank and recycles, lower floor enters the sulfuric acid densifying tower, carries sulfuric acid after dense and returns sulfuric acid absorption tower and recycle.
Example two
With 1.65 tons of C-4-fraction (iso-butylenes 45% that do not contain divinyl, Trimethylmethane 3%, 1-butylene 25%, normal butane 11%, anti-2-butylene 9%, suitable 2-butylene 7% and 1,3-divinyl＜0.5%) and 3.0 ton of 50% sulfuric acid be raw material, temperature of reaction 15-40 ℃ and pressure 0.12-0.45Mpa enter sulfuric acid absorption tower respectively and carry out esterification.Mixture (the sulfuric acid tert-butyl ester of reaction, the trimethyl carbinol and contain iso-butylene amount raffinate seldom) enter separator and separate, lower floor's mixture (sulfuric acid tert-butyl ester, the trimethyl carbinol) enters the flashing tower flash distillation, remove the hydrocarbon compound of trace, the mixture that obtains (total content of the sulfuric acid tert-butyl ester and the trimethyl carbinol reaches more than 99% by analysis) enters mixing tank and mixes from the trichloromethane of solvent tank, mixed solution enters carbonylation reactor, in carbonylation reactor, add 4.3 ton of 85% sulfuric acid simultaneously, temperature of reaction 20-30 ℃ and pressure 4.5-5.5Mpa carry out carbonylation reaction, (the sulfuric acid tert-butyl ester carbonylation product of mixture behind the carbonylation reaction, the trimethyl carbinol, trichloromethane, sulfuric acid) enter hydrolysis reactor, and in hydrolysis reactor, add frozen water, temperature of reaction 5-15 ℃ and the pressure 0.1-0.5Mpa reaction that is hydrolyzed, reaction product enters separator, upper strata trichloromethane layer enters light phase storage tank, lower aqueous layer enters the heavy phase storage tank, after enter the extraction tower chloroform extraction, upper strata trichloromethane layer after the extraction gets 1 ton of product with light storage tank mixture mutually after refining, through stratographic analysis is trimethylacetic acid more than 99%, the solvent trichloromethane returns solvent tank and recycles, lower floor enters the sulfuric acid densifying tower, carries sulfuric acid after dense and returns sulfuric acid absorption tower and recycle.
Example three
With 1.65 tons of C-4-fraction (iso-butylenes 45% that do not contain divinyl, Trimethylmethane 3%, 1-butylene 25%, normal butane 11%, anti-2-butylene 9%, suitable 2-butylene 7% and 1,3-divinyl＜0.5%) and 2.7 ton of 50% sulfuric acid be raw material, temperature of reaction 10-15 ℃ and pressure 0.1-0.12Mpa enter sulfuric acid absorption tower respectively and carry out esterification.Mixture (the sulfuric acid tert-butyl ester of reaction, the trimethyl carbinol and contain iso-butylene amount raffinate seldom) enter separator and separate, lower floor's mixture (sulfuric acid tert-butyl ester, the trimethyl carbinol) enters the flashing tower flash distillation, remove the hydrocarbon compound of trace, the mixture that obtains (total content of the sulfuric acid tert-butyl ester and the trimethyl carbinol reaches more than 99% by analysis) enters mixing tank and mixes from the trichloromethane of solvent tank, mixed solution enters carbonylation reactor, in carbonylation reactor, add 4.3 ton of 85% sulfuric acid simultaneously, temperature of reaction 20-30 ℃ and pressure 4.5-5.5Mpa carry out carbonylation reaction, (the sulfuric acid tert-butyl ester carbonylation product of mixture behind the carbonylation reaction, the trimethyl carbinol, trichloromethane, sulfuric acid) enter hydrolysis reactor, and in hydrolysis reactor, add frozen water, temperature of reaction 5-15 ℃ and the pressure 0.1-0.5Mpa reaction that is hydrolyzed, reaction product enters separator, upper strata trichloromethane layer enters light phase storage tank, lower aqueous layer enters the heavy phase storage tank, after enter the extraction tower chloroform extraction, upper strata trichloromethane layer after the extraction gets 1 ton of product with light storage tank mixture mutually after refining, through stratographic analysis is trimethylacetic acid more than 99%, the solvent trichloromethane returns solvent tank and recycles, lower floor enters the sulfuric acid densifying tower, carries sulfuric acid after dense and returns sulfuric acid absorption tower and recycle.
Example four
With 1.65 tons of C-4-fraction (iso-butylenes 45% that do not contain divinyl, Trimethylmethane 3%, 1-butylene 25%, normal butane 11%, anti-2-butylene 9%, suitable 2-butylene 7% and 1,3-divinyl＜0.5%) and 2.7 ton of 50% sulfuric acid be raw material, temperature of reaction 40-90 ℃ and pressure 0.45-2.0Mpa enter sulfuric acid absorption tower respectively and carry out esterification.Mixture (the sulfuric acid tert-butyl ester of reaction, the trimethyl carbinol and contain iso-butylene amount raffinate seldom) enter separator and separate, lower floor's mixture (sulfuric acid tert-butyl ester, the trimethyl carbinol) enters the flashing tower flash distillation, remove the hydrocarbon compound of trace, the mixture that obtains (total content of the sulfuric acid tert-butyl ester and the trimethyl carbinol reaches more than 99% by analysis) enters mixing tank and mixes from the trichloromethane of solvent tank, mixed solution enters carbonylation reactor, in carbonylation reactor, add 4.3 ton of 85% sulfuric acid simultaneously, temperature of reaction 20-30 ℃ and pressure 4.5-5.5Mpa carry out carbonylation reaction, (the sulfuric acid tert-butyl ester carbonylation product of mixture behind the carbonylation reaction, the trimethyl carbinol, trichloromethane, sulfuric acid) enter hydrolysis reactor, and in hydrolysis reactor, add frozen water, temperature of reaction 5-15 ℃ and the pressure 0.1-0.5Mpa reaction that is hydrolyzed, reaction product enters separator, upper strata trichloromethane layer enters light phase storage tank, lower aqueous layer enters the heavy phase storage tank, after enter the extraction tower chloroform extraction, upper strata trichloromethane layer after the extraction gets 1 ton of product with light storage tank mixture mutually after refining, through stratographic analysis is trimethylacetic acid more than 99%, the solvent trichloromethane returns solvent tank and recycles, lower floor enters the sulfuric acid densifying tower, carries sulfuric acid after dense and returns sulfuric acid absorption tower and recycle.
Example five
With 1.65 tons of C-4-fraction (iso-butylenes 45% that do not contain divinyl, Trimethylmethane 3%, 1-butylene 25%, normal butane 11%, anti-2-butylene 9%, suitable 2-butylene 7% and 1,3-divinyl＜0.5%) and 2.7 ton of 50% sulfuric acid be raw material, temperature of reaction 15-40 ℃ and pressure 0.12-0.45Mpa enter sulfuric acid absorption tower respectively and carry out esterification.Mixture (the sulfuric acid tert-butyl ester of reaction, the trimethyl carbinol and contain iso-butylene amount raffinate seldom) enter separator and separate, lower floor's mixture (sulfuric acid tert-butyl ester, the trimethyl carbinol) enters the flashing tower flash distillation, remove the hydrocarbon compound of trace, the mixture that obtains (total content of the sulfuric acid tert-butyl ester and the trimethyl carbinol reaches more than 99% by analysis) enters mixing tank and mixes from the trichloromethane of solvent tank, mixed solution enters carbonylation reactor, in carbonylation reactor, add 4.3 ton of 85% sulfuric acid simultaneously, temperature of reaction 0-20 ℃ and pressure 1.0-4.5Mpa carry out carbonylation reaction, (the sulfuric acid tert-butyl ester carbonylation product of mixture behind the carbonylation reaction, the trimethyl carbinol, trichloromethane, sulfuric acid) enter hydrolysis reactor, and in hydrolysis reactor, add frozen water, temperature of reaction 5-15 ℃ and the pressure 0.1-0.5Mpa reaction that is hydrolyzed, reaction product enters separator, upper strata trichloromethane layer enters light phase storage tank, lower aqueous layer enters the heavy phase storage tank, after enter the extraction tower chloroform extraction, upper strata trichloromethane layer after the extraction gets 1 ton of product with light storage tank mixture mutually after refining, through stratographic analysis is trimethylacetic acid more than 99%, the solvent trichloromethane returns solvent tank and recycles, lower floor enters the sulfuric acid densifying tower, carries sulfuric acid after dense and returns sulfuric acid absorption tower and recycle.
Example six
With 1.65 tons of C-4-fraction (iso-butylenes 45% that do not contain divinyl, Trimethylmethane 3%, 1-butylene 25%, normal butane 11%, anti-2-butylene 9%, suitable 2-butylene 7% and 1,3-divinyl＜0.5%) and 2.7 ton of 50% sulfuric acid be raw material, temperature of reaction 15-40 ℃ and pressure 0.12-0.45Mpa enter sulfuric acid absorption tower respectively and carry out esterification.Mixture (the sulfuric acid tert-butyl ester of reaction, the trimethyl carbinol and contain iso-butylene amount raffinate seldom) enter separator and separate, lower floor's mixture (sulfuric acid tert-butyl ester, the trimethyl carbinol) enters the flashing tower flash distillation, remove the hydrocarbon compound of trace, the mixture that obtains (total content of the sulfuric acid tert-butyl ester and the trimethyl carbinol reaches more than 99% by analysis) enters mixing tank and mixes from the trichloromethane of solvent tank, mixed solution enters carbonylation reactor, in carbonylation reactor, add 4.3 ton of 85% sulfuric acid simultaneously, temperature of reaction 30-100 ℃ and pressure 5.5-8.0pa carry out carbonylation reaction, (the sulfuric acid tert-butyl ester carbonylation product of mixture behind the carbonylation reaction, the trimethyl carbinol, trichloromethane, sulfuric acid) enter hydrolysis reactor, and in hydrolysis reactor, add frozen water, temperature of reaction 5-15 ℃ and the pressure 0.1-0.5Mpa reaction that is hydrolyzed, reaction product enters separator, upper strata trichloromethane layer enters light phase storage tank, lower aqueous layer enters the heavy phase storage tank, after enter the extraction tower chloroform extraction, upper strata trichloromethane layer after the extraction gets 1 ton of product with light storage tank mixture mutually after refining, through stratographic analysis is trimethylacetic acid more than 99%, the solvent trichloromethane returns solvent tank and recycles, lower floor enters the sulfuric acid densifying tower, carries sulfuric acid after dense and returns sulfuric acid absorption tower and recycle.
Example seven
With 1.65 tons of C-4-fraction (iso-butylenes 45% that do not contain divinyl, Trimethylmethane 3%, 1-butylene 25%, normal butane 11%, anti-2-butylene 9%, suitable 2-butylene 7% and 1,3-divinyl＜0.5%) and 2.7 ton of 50% sulfuric acid be raw material, temperature of reaction 15-40 ℃ and pressure 0.12-0.45Mpa enter sulfuric acid absorption tower respectively and carry out esterification.Mixture (the sulfuric acid tert-butyl ester of reaction, the trimethyl carbinol and contain iso-butylene amount raffinate seldom) enter separator and separate, lower floor's mixture (sulfuric acid tert-butyl ester, the trimethyl carbinol) enters the flashing tower flash distillation, remove the hydrocarbon compound of trace, the mixture that obtains (total content of the sulfuric acid tert-butyl ester and the trimethyl carbinol reaches more than 99% by analysis) enters mixing tank and mixes from the trichloromethane of solvent tank, mixed solution enters carbonylation reactor, in carbonylation reactor, add 4.3 ton of 85% sulfuric acid simultaneously, temperature of reaction 20-30 ℃ and pressure 4.5-5.5Mpa carry out carbonylation reaction, (the sulfuric acid tert-butyl ester carbonylation product of mixture behind the carbonylation reaction, the trimethyl carbinol, trichloromethane, sulfuric acid) enter hydrolysis reactor, and in hydrolysis reactor, add frozen water, temperature of reaction 0-5 ℃ and the pressure 0-0.1Mpa reaction that is hydrolyzed, reaction product enters separator, upper strata trichloromethane layer enters light phase storage tank, lower aqueous layer enters the heavy phase storage tank, after enter the extraction tower chloroform extraction, upper strata trichloromethane layer after the extraction gets 1 ton of product with light storage tank mixture mutually after refining, through stratographic analysis is trimethylacetic acid more than 99%, the solvent trichloromethane returns solvent tank and recycles, lower floor enters the sulfuric acid densifying tower, carries sulfuric acid after dense and returns sulfuric acid absorption tower and recycle.
Example eight
With 1.65 tons of C-4-fraction (iso-butylenes 45% that do not contain divinyl, Trimethylmethane 3%, 1-butylene 25%, normal butane 11%, anti-2-butylene 9%, suitable 2-butylene 7% and 1,3-divinyl＜0.5%) and 2.7 ton of 50% sulfuric acid be raw material, temperature of reaction 15-40 ℃ and pressure 0.12-0.45Mpa enter sulfuric acid absorption tower respectively and carry out esterification.Mixture (the sulfuric acid tert-butyl ester of reaction, the trimethyl carbinol and contain iso-butylene amount raffinate seldom) enter separator and separate, lower floor's mixture (sulfuric acid tert-butyl ester, the trimethyl carbinol) enters the flashing tower flash distillation, remove the hydrocarbon compound of trace, the mixture that obtains (total content of the sulfuric acid tert-butyl ester and the trimethyl carbinol reaches more than 99% by analysis) enters mixing tank and mixes from the trichloromethane of solvent tank, mixed solution enters carbonylation reactor, in carbonylation reactor, add 4.3 ton of 85% sulfuric acid simultaneously, temperature of reaction 20-30 ℃ and pressure 4.5-5.5Mpa carry out carbonylation reaction, (the sulfuric acid tert-butyl ester carbonylation product of mixture behind the carbonylation reaction, the trimethyl carbinol, trichloromethane, sulfuric acid) enter hydrolysis reactor, and in hydrolysis reactor, add frozen water, temperature of reaction 15-100 ℃ and the pressure 0.5-1.0Mpa reaction that is hydrolyzed, reaction product enters separator, upper strata trichloromethane layer enters light phase storage tank, lower aqueous layer enters the heavy phase storage tank, after enter the extraction tower chloroform extraction, upper strata trichloromethane layer after the extraction gets 1 ton of product with light storage tank mixture mutually after refining, through stratographic analysis is trimethylacetic acid more than 99%, the solvent trichloromethane returns solvent tank and recycles, lower floor enters the sulfuric acid densifying tower, carries sulfuric acid after dense and returns sulfuric acid absorption tower and recycle.
Example nine
With 1.65 tons of C-4-fraction (iso-butylenes 45% that do not contain divinyl, Trimethylmethane 3%, 1-butylene 25%, normal butane 11%, anti-2-butylene 9%, suitable 2-butylene 7% and 1,3-divinyl＜0.5%) and 3 ton of 45% sulfuric acid be raw material, temperature of reaction 15-40 ℃ and pressure 0.12-0.45Mpa enter sulfuric acid absorption tower respectively and carry out esterification.Mixture (the sulfuric acid tert-butyl ester of reaction, the trimethyl carbinol and contain iso-butylene amount raffinate seldom) enter separator and separate, lower floor's mixture (sulfuric acid tert-butyl ester, the trimethyl carbinol) enters the flashing tower flash distillation, remove the hydrocarbon compound of trace, the mixture that obtains (total content of the sulfuric acid tert-butyl ester and the trimethyl carbinol reaches more than 99% by analysis) enters mixing tank and mixes from the trichloromethane of solvent tank, mixed solution enters carbonylation reactor, in carbonylation reactor, add 4.3 ton of 85% sulfuric acid simultaneously, temperature of reaction 20-30 ℃ and pressure 4.5-5.5Mpa carry out carbonylation reaction, (the sulfuric acid tert-butyl ester carbonylation product of mixture behind the carbonylation reaction, the trimethyl carbinol, trichloromethane, sulfuric acid) enter hydrolysis reactor, and in hydrolysis reactor, add frozen water, temperature of reaction 5-15 ℃ and the pressure 0.1-0.5Mpa reaction that is hydrolyzed, reaction product enters separator, upper strata trichloromethane layer enters light phase storage tank, lower aqueous layer enters the heavy phase storage tank, after enter the extraction tower chloroform extraction, upper strata trichloromethane layer after the extraction gets 1 ton of product with light storage tank mixture mutually after refining, through stratographic analysis is trimethylacetic acid more than 99%, the solvent trichloromethane returns solvent tank and recycles, lower floor enters the sulfuric acid densifying tower, carries sulfuric acid after dense and returns sulfuric acid absorption tower and recycle.
Example ten
With 1.65 tons of C-4-fraction (iso-butylenes 45% that do not contain divinyl, Trimethylmethane 3%, 1-butylene 25%, normal butane 11%, anti-2-butylene 9%, suitable 2-butylene 7% and 1,3-divinyl＜0.5%) and 2.08 ton of 65% sulfuric acid be raw material, temperature of reaction 15-40 ℃ and pressure 0.12-0.45Mpa enter sulfuric acid absorption tower respectively and carry out esterification.Mixture (the sulfuric acid tert-butyl ester of reaction, the trimethyl carbinol and contain iso-butylene amount raffinate seldom) enter separator and separate, lower floor's mixture (sulfuric acid tert-butyl ester, the trimethyl carbinol) enters the flashing tower flash distillation, remove the hydrocarbon compound of trace, the mixture that obtains (total content of the sulfuric acid tert-butyl ester and the trimethyl carbinol reaches more than 99% by analysis) enters mixing tank and mixes from the trichloromethane of solvent tank, mixed solution enters carbonylation reactor, in carbonylation reactor, add 4.3 ton of 85% sulfuric acid simultaneously, temperature of reaction 20-30 ℃ and pressure 4.5-5.5Mpa carry out carbonylation reaction, (the sulfuric acid tert-butyl ester carbonylation product of mixture behind the carbonylation reaction, the trimethyl carbinol, trichloromethane, sulfuric acid) enter hydrolysis reactor, and in hydrolysis reactor, add frozen water, temperature of reaction 5-15 ℃ and the pressure 0.1-0.5Mpa reaction that is hydrolyzed, reaction product enters separator, upper strata trichloromethane layer enters light phase storage tank, lower aqueous layer enters the heavy phase storage tank, after enter the extraction tower chloroform extraction, upper strata trichloromethane layer after the extraction gets 1 ton of product with light storage tank mixture mutually after refining, through stratographic analysis is trimethylacetic acid more than 99%, the solvent trichloromethane returns solvent tank and recycles, lower floor enters the sulfuric acid densifying tower, carries sulfuric acid after dense and returns sulfuric acid absorption tower and recycle.
Example 11
With 4.79 tons of C-4-fraction (iso-butylenes 15.6% that do not contain divinyl, Trimethylmethane 35.8%, 1-butylene 13.1%, normal butane 11%, anti-2-butylene 14.1%, suitable 2-butylene 10% and 1,3-divinyl＜0.4%) and 2.7 ton of 50% sulfuric acid be raw material, temperature of reaction 15-40 ℃ and pressure 0.12-0.45Mpa enter sulfuric acid absorption tower respectively and carry out esterification.Mixture (the sulfuric acid tert-butyl ester of reaction, the trimethyl carbinol and contain iso-butylene amount raffinate seldom) enter separator and separate, lower floor's mixture (sulfuric acid tert-butyl ester, the trimethyl carbinol) enters the flashing tower flash distillation, remove the hydrocarbon compound of trace, the mixture that obtains (total content of the sulfuric acid tert-butyl ester and the trimethyl carbinol reaches more than 99% by analysis) enters mixing tank and mixes from the trichloromethane of solvent tank, mixed solution enters carbonylation reactor, in carbonylation reactor, add 4.3 ton of 85% sulfuric acid simultaneously, temperature of reaction 20-30 ℃ and pressure 4.5-5.5Mpa carry out carbonylation reaction, (the sulfuric acid tert-butyl ester carbonylation product of mixture behind the carbonylation reaction, the trimethyl carbinol, trichloromethane, sulfuric acid) enter hydrolysis reactor, and in hydrolysis reactor, add frozen water, temperature of reaction 5-15 ℃ and the pressure 0.1-0.5Mpa reaction that is hydrolyzed, reaction product enters separator, upper strata trichloromethane layer enters light phase storage tank, lower aqueous layer enters the heavy phase storage tank, after enter the extraction tower chloroform extraction, upper strata trichloromethane layer after the extraction gets 1 ton of product with light storage tank mixture mutually after refining, through stratographic analysis is trimethylacetic acid more than 99%, the solvent trichloromethane returns solvent tank and recycles, lower floor enters the sulfuric acid densifying tower, carries sulfuric acid after dense and returns sulfuric acid absorption tower and recycle.
Claims (12)
1. method of producing trimethylacetic acid, this method comprises the steps:
A. the C-4-fraction that does not contain divinyl and sulfuric acid are mixed, be enough to carry out to carry out esterification under the temperature and pressure of esterification, through separating to such an extent that be substantially free of raffinate and lower floor's mixture of iso-butylene to the upper strata;
B. lower floor's mixture and carbon monoxide are carried out carbonylation reaction, after hydrolysis reaction, separation, make the trimethylacetic acid finished product.
2. the method for production trimethylacetic acid as claimed in claim 1 is characterized in that: the mass content that does not contain iso-butylene in the C-4-fraction of divinyl is 10%-50%.
3. the method for production trimethylacetic acid as claimed in claim 2 is characterized in that: the mass content that does not contain iso-butylene in the C-4-fraction of divinyl is 40%-50%.
4. the method for production trimethylacetic acid as claimed in claim 3 is characterized in that: the mass content that does not contain iso-butylene in the C-4-fraction of divinyl is 45%.
5. the method for production trimethylacetic acid as claimed in claim 1 is characterized in that: do not contain that quality of butadiene content is lower than 0.5% in the C-4-fraction of divinyl.
6. the method for production trimethylacetic acid as claimed in claim 1 is characterized in that: the temperature during esterification is 10-90 ℃, and pressure is 0.1-2.0Mpa; Temperature during carbonylation reaction is 0-100 ℃, and pressure is 1.0-8.0Mpa; Temperature during hydrolysis reaction is 0-100 ℃, and pressure is 0-1.0Mpa.
7. the method for production trimethylacetic acid as claimed in claim 6 is characterized in that: the temperature during esterification is 40-50 ℃, and pressure is 0.12-0.45Mpa.
8. the method for production trimethylacetic acid as claimed in claim 6 is characterized in that: the temperature during carbonylation reaction is 20-30 ℃, and pressure is 4.5-5.5Mpa.
9. the method for production trimethylacetic acid as claimed in claim 6 is characterized in that: the temperature during hydrolysis reaction is 5-15 ℃, and pressure is 0.1-0.5Mpa.
10. the method for production trimethylacetic acid as claimed in claim 1 is characterized in that: in carbonylation reaction, use H
2SO
4System is as catalyzer.
11. the method as each described production trimethylacetic acid among the claim 1-10 is characterized in that: in carbonylation reaction, use trichloromethane as solvent.
12. the method for claim 1 is characterized in that: wherein directly as the raw material of esterification, another part recycles as the carbonylation reaction raw material after concentrating the part of the dilute sulphuric acid behind the hydrolysis reaction.
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| CN101838192A (en) * | 2010-05-26 | 2010-09-22 | 天津大学 | Trimethylacetic acid crude product refining process and device |
| CN104058948B (en) * | 2014-07-03 | 2016-01-27 | 河北华旭化工有限公司 | The method of reclaim(ed) sulfuric acid and trimethylacetic acid from the spent acid of trimethylacetic acid building-up process by-product |
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| 液相催化科克合成特戊酸及其动力学研究. 陈国英.河北工业大学硕士学位论文. 2002 * |
| 羰基合成特戊酸工艺技术改进. 黄斌.上海化工，第5期. 2004 * |
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