CN104892410B - A kind of methyl acrylate waste oil recovery process - Google Patents
A kind of methyl acrylate waste oil recovery process Download PDFInfo
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- CN104892410B CN104892410B CN201510206892.5A CN201510206892A CN104892410B CN 104892410 B CN104892410 B CN 104892410B CN 201510206892 A CN201510206892 A CN 201510206892A CN 104892410 B CN104892410 B CN 104892410B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/60—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/62—Use of additives, e.g. for stabilisation
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Abstract
The invention discloses a kind of methyl acrylate waste oil recovery process, washes including depolymerization, esterification, salt, takes off five step of light, de- weight.Methyl acrylate waste oil recovery process of the present invention is by being washed using depolymerization, esterification, salt, de- light, de- weight process is recycled to acrylic acid waste oil and methyl acrylate waste oil, the high efficiente callback to methyl acrylate can be realized, the purity of finished product is higher, after testing according to the technique productions finished product methyl acrylate purity up to more than 99.4.
Description
Technical field
The present invention relates to acrylate waste oil reclaims field, and in particular to a kind of methyl acrylate waste oil recovery process.
Background technology
Methyl acrylate is a kind of important synthetic intermediate, and the monomer of synthesising macromolecule copolymer, is widely used in
Rubber, medicine, leather, papermaking, adhesive and coating industry.Produce in the production process of acrylic acid and esters of acrylic acid at present
Waste oil amount increases, and needs corresponding process.Main component in methyl acrylate waste oil be methyl acrylate, acrylic acid, methyl alcohol,
Water and methoxy-methyl acrylate etc..In prior art the recovery of methyl acrylate mainly include cracking, be esterified, de- light and de-
Weigh four operations.A kind of recovery dress of the i.e. esters of acrylic acid waste oil of acrylic acid is disclosed in Chinese patent 200820214814.5
Put, the cracking that wherein refers to, esterification, neutralization, washing, de- light, de- weight, the technique are applied to butyl acrylate and 2-ethyl hexyl acrylate
Recovery；One kind is disclosed in CN101239909B（Methyl）The manufacture method of acrylate, removes acid catalysis including esterification, washing
The operations such as agent, neutralization.
Methyl acrylate contains unstable carbon-carbon double bond, is easy to addition reaction during production storage, light,
Heat and peroxide can accelerate its polymerization, it usually needs the carrying out for preventing polymerization using polymerization inhibitor.Variety classes
The polymerization inhibitor mechanism of action differ：Its of phenolic inhibitor inhibits the free radical that mechanism is that phenols is oxidized to corresponding quinone and chain
In conjunction with and rise inhibition；Inorganic salts are by electric charge transfer and to play inhibition, and iron chloride inhibits efficiency high, and can press chemistry
Dosage 1：1 eliminates free radical.One kind is disclosed in CN102173990A, and butyl acrylate is prepared as polymerization inhibitor using phenthazine
Method, but by phenthazine be used for methyl acrylate polymerization inhibition effect undesirable, in prior art methyl acrylate reclaim yield
Relatively low with finished product purity.Therefore, it is necessary to be improved to methyl acrylate recovery process of the prior art.
Content of the invention
It is an object of the invention to overcoming the defect of prior art, there is provided a kind of methyl acrylate reclaims yield and finished product is pure
The higher methyl acrylate waste oil recovery process of degree.
For achieving the above object, the technical scheme is that a kind of methyl acrylate waste oil recovery process, its feature exist
In comprising the following steps：
S1：Depolymerization, after methyl acrylate waste oil, acrylic acid waste oil, esterified acid catalyst and methyl alcohol are warming up to de-polymerization temperature
Insulation reaction, reaction are distilled to gained depolymerization mixed liquor after terminating, and main component is methyl acrylate, the mixing of first alcohol and water
Steam is condensed, obtains depolymerization mixed liquor；
S2：Esterification, depolymerization mixed liquor, methyl alcohol, acrylic acid, esterified acid catalyst are warming up to esterification temperature and carry out being esterified instead
Should, rectifying, steam condensation, stratification is carried out to being esterified gained esterification reaction solution, obtain oil phase esterification mixed liquor；
S3：Salt is washed, and by sodium chloride, inorganic polymerization inhibitor is soluble in water is configured to saturated brine, goes oil removing using saturated brine
The methyl alcohol being mutually esterified in batch mixing, stratification obtain salt solution mother liquor and remove alcohol esterification liquid；
S4：De- light, to going alcohol esterification liquid intensification vacuum distillation, main component to distillate for methyl alcohol, methyl acrylate and water
Steam is condensed, stratification must take off light esterifying liquid；
S5：De- weight, to taking off light esterifying liquid intensification vacuum distillation, main component distillates steam through cold for methyl acrylate
Solidifying, obtain methyl acrylate finished product.
In order that the raw material in production system is realized applying mechanically, it is ensured that higher methyl acrylate reclaims yield, preferred skill
Art scheme is that the salt solution mother liquor obtains recovered brine through disposing mother liquor operation and reclaims alcohol ester, and recovered brine is applied to salt and washes work
Sequence, reclaims alcohol ester and is applied to depolymerization operation, and the disposing mother liquor operation is by the air-distillation at 70～73 DEG C of salt solution mother liquor, obtains
Vinasse and distillate steam, described distillate that steam is condensed must to reclaim alcohol ester, vinasse is recovered brine.
Preferred technical scheme is that the de-polymerization temperature in the S1 is 145～155 DEG C；In the S2, esterification temperature is 105
～125 DEG C；The de- light process conditions are 57～63 DEG C, -0.045～-0.035MPa of negative pressure；The process conditions of the de- weight
For 67～73 DEG C, -0.045～-0.035MPa of negative pressure.
Acrylic acid and ester gas phase easily occur being polymerized when condensing on condensing tower or pipeline, in order to avoid condenser and with cold
Occurs material polymerism in the reactor that condenser is communicated, preferred technical scheme is that the condenser top in depolymerization operation adds
The depolymerization inhibitor solution that depolymerization mixed liquor is mixed with polymerization inhibitor；Condenser top in the esterification step adds oil phase ester
Change the esterification inhibitor solution that mixed liquor is mixed with polymerization inhibitor；Condenser top in the de- light industry sequence adds de- light esterification
The de- light inhibitor solution that liquid is mixed with polymerization inhibitor；Condenser top in the de- heavy industry sequence adds methyl acrylate finished product
The de- heavy inhibitor solution mixed with polymerization inhibitor.After the inhibitor solution of condenser top spray and vapor condensation
Material mixes, and prevents condensed material polymerization, and by spraying the attachment that can be washed away in condenser tube side.
Preferred technical scheme is, the depolymerization inhibitor solution, esterification inhibitor solution, takes off light inhibitor solution, de-
Polymerization inhibitor in weight inhibitor solution is at least one in phenthazine, hydroquinones, MEHQ.Above-mentioned inhibition
Agent is dissolved in the organic solvent of acrylic acid and ester, and with stronger polymerization inhibiting capacity.
The polymerization activity of acrylic acid and methyl acrylate is stronger, and hydroquinones inhibition activity is relatively strong, can be under the high temperature conditions
Polymerization inhibition effect good, under anaerobic have weaker polymerization inhibiting capacity, phenthazine be the acrylic acid by attack electron deficient and
Ester free radical generates stable phenthazine free radical.In depolymerization condenser, acrylic acid concentration is higher, acrylic acid sterically hindered compared with
Little, it is more vulnerable to the attack of free radical；In addition, hydroquinones and phenthazine de- process again in residue in de- heavy residue with into
Product are separated, and in order to further optimize the polymerization inhibition effect of depolymerization operation, preferred technical scheme is, in the depolymerization inhibitor solution
Polymerization inhibitor be hydroquinones and phenthazine composition, the weight hundred of hydroquinones in the depolymerization inhibitor solution polymerization inhibitor
Divide than being 50～65%, in the depolymerization inhibitor solution, the weight of polymerization inhibitor with depolymerization operation condensate liquid weight ratio is（1～
15）：10000.
After esterification, acrylic acid content reduces, in order to optimize the polymerization inhibition effect of esterification step, preferred technical scheme
For the polymerization inhibitor in the esterification inhibitor solution is hydroquinones and the composition of phenthazine, the esterification inhibitor solution
In polymerization inhibitor, the percentage by weight of hydroquinones is 55～75%, the weight of polymerization inhibitor and esterification in the esterification inhibitor solution
Operation condensate liquid weight ratio is（1～15）：10000.
Layered shaping after esterification condensation makes acrylic acid, water etc. separate with oil phase esterification mixed liquor, therefore takes off light process
Mixture be practically free of acrylic acid or content seldom, the polymerization inhibition effect rapid in order to optimize de- fox trot described takes off light polymerization inhibitor
Polymerization inhibitor in solution is the composition of hydroquinones and phenthazine, hydroquinones in the de- light inhibitor solution polymerization inhibitor
Percentage by weight is 60～80%, and in the de- light inhibitor solution, the weight of polymerization inhibitor with alcohol esterification liquid weight ratio is removed is（2
～16）：10000.
The polymerization inhibition performance of hydroquinones and phenthazine is better than MEHQ, and is not easily decomposed, and is mixed in finished product and is difficult
Separate, in order to avoid polymerization inhibitor is using end properties is affected, preferred technical scheme is, in the de- heavy inhibitor solution
Polymerization inhibitor be MEHQ, in the de- heavy inhibitor solution, the weight of polymerization inhibitor with de- light esterifying liquid weight ratio is
（0.5～14）：10000.
Preferred technical scheme can also be that the inorganic polymerization inhibitor in the S3 is in copper sulphate or ferrous sulfate
At least one, the weight of the inorganic polymerization inhibitor are to be with oil phase esterification mixed liquor weight ratio（5～30）：10000.
The advantages of the present invention are：
Methyl acrylate waste oil recovery process of the present invention is by being washed using depolymerization, esterification, salt, de- light, the technique side of de- weight
Method is recycled to acrylic acid waste oil and methyl acrylate waste oil, can realize the high efficiente callback to methyl acrylate, finished product
Purity higher, after testing according to the technique productions finished product methyl acrylate purity up to more than 99.4.
Specific embodiment
With reference to embodiment, the specific embodiment of the present invention is further described.Following examples are only used for more
Plus technical scheme is clearly demonstrated, and can not be limited the scope of the invention with this.
Embodiment 1
The raw material of 1 methyl acrylate waste oil recovery process of embodiment is methyl acrylate waste oil and acrylic acid waste oil, propylene
Sour methyl esters waste oil group is divided into acrylic acid 40.04%, methyl acrylate 20.38%, methyl alcohol 8.1%, water 2.93%, ethyl acrylate
0.19% and 3- methoxy-methyl acrylate 28.36%, the composition of acrylic acid waste oil be acrylic acid dimer 38.52%, water 5.8%,
Acrylic acid 55.68%, methyl acrylate waste oil are 7 with the ratio of the inventory of acrylic acid waste oil:1, put into excessive methyl alcohol and solved
Poly- reaction.
S1：Methyl acrylate waste oil, acrylic acid waste oil, esterified acid catalyst and methyl alcohol are added depolymerization unit by depolymerization, are risen
Temperature is distilled to gained depolymerization mixed liquor after terminating to 150 DEG C of insulation reactions, reaction, and main component is methyl acrylate, first
Alcohol and water mixed vapour is condensed, obtains depolymerization mixed liquor；
It is two molecule acrylic acid, acrylic acid and methyl alcohol ester that the main reaction of depolymerization operation is a molecule acrylic acid dimer depolymerization
Change reaction and generate methyl acrylate；
S2：Esterification, depolymerization mixed liquor, methyl alcohol, acrylic acid, esterified acid catalyst are warming up to esterification temperature and carry out being esterified instead
Should, rectifying, steam condensation, stratification is carried out to being esterified gained esterification reaction solution, obtain oil phase esterification mixed liquor；
Using p-methyl benzenesulfonic acid as esterified acid catalyst, main reaction in esterification step is that methyl alcohol and acroleic acid esterification are generated
Methyl acrylate, side reaction are that methyl acrylate generates 2 hydroxy propanoic acid N-butyl, methyl acrylate and first with water addition reaction
Alcohol reaction generates 3- methoxy methyl propionates；
S3：Salt is washed, and by sodium chloride, inorganic polymerization inhibitor is soluble in water is configured to saturated brine, goes oil removing using saturated brine
The methyl alcohol being mutually esterified in batch mixing, stratification obtain salt solution mother liquor and remove alcohol esterification liquid；
S4：De- light, to going alcohol esterification liquid to be warming up to 60 DEG C, vacuum distillation under negative pressure -0.04MPa, main component are first
Alcohol, methyl acrylate and water distillate that steam is condensed, stratification must take off light esterifying liquid；
S5：De- weight, is warming up to 70 DEG C to taking off light esterifying liquid, and vacuum distillation under negative pressure -0.04MPa, main component are third
E pioic acid methyl ester to distillate steam condensed, obtain methyl acrylate finished product.
The main component of salt solution mother liquor is in addition to sodium chloride, copper sulphate and water, also containing methyl alcohol and a small amount of acrylic acid first
Ester, obtains recovered brine through disposing mother liquor operation and reclaims alcohol ester, and recovered brine is applied to salt and washes operation, reclaims alcohol ester and is applied to solve
Poly- operation, disposing mother liquor operation are by the air-distillation at 70～73 DEG C of salt solution mother liquor, obtain vinasse and distillate steam, distillate
Steam is condensed must to reclaim alcohol ester, and vinasse is recovered brine.
Condenser top in depolymerization operation adds the depolymerization polymerization inhibitor that depolymerization mixed liquor is mixed with MEHQ
Solution；Condenser top in esterification step adds the esterification polymerization inhibitor that oil phase esterification mixed liquor is mixed with MEHQ
Solution；Condenser top in de- light industry sequence adds de- light esterifying liquid molten with the de- light polymerization inhibitor that MEHQ is mixed
Liquid；Condenser top in de- heavy industry sequence adds methyl acrylate finished product molten with the de- heavy polymerization inhibitor that MEHQ is mixed
Liquid, MEHQ in depolymerization inhibitor solution, esterification inhibitor solution, de- light inhibitor solution and de- weight inhibitor solution
Weight be 7 with de- light esterifying liquid weight ratio：10000.
Inorganic polymerization inhibitor is ferrous sulfate, and the weight of inorganic polymerization inhibitor is to be esterified mixed liquor weight ratio for 5 with oil phase：
10000.
Embodiment 2
Embodiment 2 is with the difference of embodiment 1：In S1, de-polymerization temperature is 145 DEG C；In S2, the esterification temperature of esterification is
105℃；De- light process conditions are 57 DEG C, negative pressure -0.045；The process conditions of de- weight are 67 DEG C, negative pressure -0.045MPa.
Embodiment 3
Embodiment 3 is with the difference of embodiment 1：De-polymerization temperature in S1 is 145～155 DEG C；Temperature is esterified in the S2
Spend for 125 DEG C；The de- light process conditions are 63 DEG C, negative pressure -0.035MPa；The process conditions of the de- weight are 73 DEG C, bear
Pressure -0.035MPa.
Embodiment 4
Embodiment 4 is with the difference of embodiment 1：Depolymerization inhibitor solution, esterification inhibitor solution, de- light polymerization inhibitor are molten
Polymerization inhibitor in liquid, de- weight inhibitor solution is the composition of hydroquinones and phenthazine, depolymerization inhibitor solution polymerization inhibitor
The percentage by weight of middle hydroquinones is 50%, the weight of polymerization inhibitor and depolymerization operation condensate liquid weight in depolymerization inhibitor solution
Ratio be 1：10000；In esterification inhibitor solution polymerization inhibitor, the percentage by weight of hydroquinones is 55%, is esterified inhibitor solution
The weight of middle polymerization inhibitor is 1 with esterification step condensate liquid weight ratio：10000；Take off in light inhibitor solution polymerization inhibitor to benzene two
The percentage by weight of phenol be 60%, take off light inhibitor solution in polymerization inhibitor weight with go alcohol esterification liquid weight ratio be 2：
10000；Polymerization inhibitor in de- weight inhibitor solution is MEHQ, take off in weight inhibitor solution the weight of polymerization inhibitor with de-
Light esterifying liquid weight ratio is 0.5：10000.
Inorganic polymerization inhibitor is copper sulphate, and the weight of inorganic polymerization inhibitor is to be esterified mixed liquor weight ratio for 18 with oil phase：
10000.
Embodiment 5
Embodiment 5 is with the difference of embodiment 4：Depolymerization inhibitor solution, esterification inhibitor solution, de- light polymerization inhibitor are molten
Polymerization inhibitor in liquid, de- weight inhibitor solution is the composition of hydroquinones and phenthazine, depolymerization inhibitor solution polymerization inhibitor
The percentage by weight of middle hydroquinones is 65%, the weight of polymerization inhibitor and depolymerization operation condensate liquid weight in depolymerization inhibitor solution
Ratio be 15：10000；In esterification inhibitor solution polymerization inhibitor, the percentage by weight of hydroquinones is 75%, is esterified inhibitor solution
The weight of middle polymerization inhibitor is 15 with esterification step condensate liquid weight ratio：10000；Take off in light inhibitor solution polymerization inhibitor to benzene two
The percentage by weight of phenol be 80%, take off light inhibitor solution in polymerization inhibitor weight with go alcohol esterification liquid weight ratio be 16：
10000；Polymerization inhibitor in de- weight inhibitor solution is MEHQ, take off in weight inhibitor solution the weight of polymerization inhibitor with de-
Light esterifying liquid weight ratio is 14：10000.
Embodiment 6
Embodiment 6 is with the difference of embodiment 4：Depolymerization inhibitor solution, esterification inhibitor solution, de- light polymerization inhibitor are molten
Polymerization inhibitor in liquid, de- weight inhibitor solution is the composition of hydroquinones and phenthazine, depolymerization inhibitor solution polymerization inhibitor
The percentage by weight of middle hydroquinones is 57%, the weight of polymerization inhibitor and depolymerization operation condensate liquid weight in depolymerization inhibitor solution
Ratio be 8：10000；In esterification inhibitor solution polymerization inhibitor, the percentage by weight of hydroquinones is 68%, is esterified inhibitor solution
The weight of middle polymerization inhibitor is 7 with esterification step condensate liquid weight ratio：10000；Take off in light inhibitor solution polymerization inhibitor to benzene two
The percentage by weight of phenol be 70%, take off light inhibitor solution in polymerization inhibitor weight with go alcohol esterification liquid weight ratio be 9：
10000；Polymerization inhibitor in de- weight inhibitor solution is MEHQ, take off in weight inhibitor solution the weight of polymerization inhibitor with de-
Light esterifying liquid weight ratio is 6：10000.
Embodiment 7
Embodiment 7 is with the difference of embodiment 6：Depolymerization inhibitor solution, esterification inhibitor solution, de- light polymerization inhibitor are molten
Polymerization inhibitor in liquid, de- weight inhibitor solution is hydroquinones, and the consumption of each step hydroquinones is same as Example 6.
Inorganic polymerization inhibitor is copper sulphate, and the weight of inorganic polymerization inhibitor is to be esterified mixed liquor weight ratio for 30 with oil phase：
10000.
Embodiment 8
Embodiment 8 is with the difference of embodiment 6：Depolymerization inhibitor solution, esterification inhibitor solution, de- light polymerization inhibitor are molten
Polymerization inhibitor in liquid, de- weight inhibitor solution is phenthazine, and the consumption of each step hydroquinones is same as Example 6.
In embodiment 1-8, inhibitor solution is added by condenser top by the way of spray, depolymerization inhibitor solution
Middle inhibitor concentration（Weight percent concentration）For 2～2.2%, inhibitor concentration in esterification inhibitor solution（Percentage by weight is dense
Degree）For 2.5～2.8%, inhibitor concentration in light inhibitor solution is taken off（Weight percent concentration）For 2.5～2.8%, de- inhibit again
Inhibitor concentration in agent solution（Weight percent concentration）For 0.9～1.2%.
Result of the test shows, in embodiment 1-3, the methyl acrylate yield of embodiment 1 is more than embodiment 2 and embodiment 3,
In embodiment 4-6, the methyl acrylate yield of embodiment 6 is larger, occurs in various degree white in the condenser of embodiment 4 and 5
, there is polymerisation in color substance, polymerization inhibition effect is poor compared with embodiment 6.In embodiment 6-8, the methyl acrylate yield of embodiment 6 compared with
Greatly, equally there is different degrees of polymerisation in embodiment 7 and 8, hydroquinones and phenthazine are used in mixed way and make polymerization inhibition effect
It is remarkably reinforced, hydroquinones and phenthazine can be removed in de- heavy industry sequence, compared with using MEHQ as polymerization inhibitor,
Cost is lower.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, on the premise of without departing from the technology of the present invention principle, some improvements and modifications can also be made, these improvements and modifications
Also protection scope of the present invention should be regarded as.
Claims (7)
1. a kind of methyl acrylate waste oil recovery process, it is characterised in that comprise the following steps：
S1：Depolymerization, methyl acrylate waste oil, acrylic acid waste oil, esterified acid catalyst and methyl alcohol are incubated after being warming up to de-polymerization temperature
Reaction, reaction are distilled to gained depolymerization mixed liquor after terminating, and main component is methyl acrylate, first alcohol and water mixed vapour
Condensed, obtain depolymerization mixed liquor； S2：Esterification, depolymerization mixed liquor, methyl alcohol, acrylic acid, esterified acid catalyst are warming up to esterification temperature
Degree carries out esterification, carries out rectifying, steam condensation, stratification to being esterified gained esterification reaction solution, obtains oil phase esterification mixing
Liquid；
S3：Salt is washed, and by sodium chloride, inorganic polymerization inhibitor is soluble in water is configured to saturated brine, removes oil phase ester using saturated brine
Change the methyl alcohol in batch mixing, stratification obtains salt solution mother liquor and removes alcohol esterification liquid；
S4：De- light, to going alcohol esterification liquid intensification vacuum distillation, main component to distillate steam for methyl alcohol, methyl acrylate and water
Condensed, stratification must take off light esterifying liquid；
S5：De- weight, to taking off light esterifying liquid intensification vacuum distillation, main component for methyl acrylate to distillate steam condensed, obtain
Methyl acrylate finished product；Condenser top in depolymerization operation adds the depolymerization polymerization inhibitor that depolymerization mixed liquor is mixed with polymerization inhibitor
Solution；Condenser top in the esterification step adds oil phase esterification mixed liquor molten with the esterification polymerization inhibitor that polymerization inhibitor is mixed
Liquid；Condenser top in the de- light industry sequence adds the de- light inhibitor solution for taking off that light esterifying liquid is mixed with polymerization inhibitor；Institute
The de- heavy inhibitor solution that the condenser top in de- heavy industry sequence adds methyl acrylate finished product to mix is stated with polymerization inhibitor；Described
Polymerization inhibitor in depolymerization inhibitor solution is the composition of hydroquinones and phenthazine, in the depolymerization inhibitor solution polymerization inhibitor
The percentage by weight of hydroquinones is 50～65%, and in the depolymerization inhibitor solution, the weight of polymerization inhibitor is condensed with depolymerization operation
Liquid weight ratio is（1～15）：10000；Polymerization inhibitor in the esterification inhibitor solution is the group of hydroquinones and phenthazine
Compound；The polymerization inhibitor taken off in light inhibitor solution is hydroquinones and the composition of phenthazine；The de- heavy polymerization inhibitor is molten
Polymerization inhibitor in liquid is MEHQ.
2. methyl acrylate waste oil recovery process according to claim 1, it is characterised in that the salt solution mother liquor is through mother liquor
Recovery process obtains recovered brine and reclaims alcohol ester, and recovered brine is applied to salt and washes operation, reclaims alcohol ester and is applied to depolymerization operation, institute
It is by the air-distillation at 70～73 DEG C of salt solution mother liquor to state disposing mother liquor operation, obtains and vinasse and distillates steam, described distillates
Steam is condensed must to reclaim alcohol ester, and vinasse is recovered brine.
3. methyl acrylate waste oil recovery process according to claim 1, it is characterised in that the de-polymerization temperature in the S1
For 145～155 DEG C；In the S2, esterification temperature is 105～125 DEG C；The de- light process conditions are 57～63 DEG C, negative pressure-
0.045～-0.035MPa；The process conditions of the de- weight are 67～73 DEG C, -0.045～-0.035MPa of negative pressure.
4. methyl acrylate waste oil recovery process according to claim 1, it is characterised in that the esterification inhibitor solution
In polymerization inhibitor, the percentage by weight of hydroquinones is 55～75%, the weight of polymerization inhibitor and esterification in the esterification inhibitor solution
Operation condensate liquid weight ratio is（1～15）：10000.
5. methyl acrylate waste oil recovery process according to claim 1, it is characterised in that described take off light inhibitor solution
In polymerization inhibitor the percentage by weight of hydroquinones be 60～80%, described take off light inhibitor solution in polymerization inhibitor weight with remove alcohol
Esterifying liquid weight ratio is（2～16）：10000.
6. methyl acrylate waste oil recovery process according to claim 1, it is characterised in that the de- heavy inhibitor solution
The weight of middle polymerization inhibitor with de- light esterifying liquid weight ratio is（0.5～14）：10000.
7. methyl acrylate waste oil recovery process according to claim 1, it is characterised in that the inorganic inhibition in the S3
Agent is at least one in copper sulphate or ferrous sulfate, and the weight of the inorganic polymerization inhibitor is to be esterified mixed liquor weight with oil phase
The ratio of amount is（5～30）：10000.
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| CN109678711B (en) * | 2017-10-19 | 2021-08-27 | 山东开泰石化股份有限公司 | System and method for extracting methyl methoxypropionate from methyl acrylate waste oil |
| CN108752200A (en) * | 2018-04-28 | 2018-11-06 | 江苏新东风化工科技有限公司 | A method of being used for acrylic acid methyl esters waste oil |
| CN108530295A (en) * | 2018-04-28 | 2018-09-14 | 江苏新东风化工科技有限公司 | A kind of technique of the acrylic acid N-butyl from waste oil |
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| CN201313874Y (en) * | 2008-12-16 | 2009-09-23 | 沈晓东 | Waste acrylic acid and acrylic ester recovery device |
| CN102173990A (en) * | 2011-03-16 | 2011-09-07 | 抚州市嘉临化工助剂厂 | Preparation method of butyl acrylate |
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| JPS5982991A (en) * | 1982-11-01 | 1984-05-14 | Nippon Zeon Co Ltd | Removing or recovering method of oil |
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| CN101239909A (en) * | 2008-03-17 | 2008-08-13 | 上海华谊丙烯酸有限公司 | Method for preparing (methyl) acrylate and device used for the same |
| CN201313874Y (en) * | 2008-12-16 | 2009-09-23 | 沈晓东 | Waste acrylic acid and acrylic ester recovery device |
| CN102173990A (en) * | 2011-03-16 | 2011-09-07 | 抚州市嘉临化工助剂厂 | Preparation method of butyl acrylate |
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