CN110372509A - A kind of cracking recovery process of n-butyl acrylate heavy constituent - Google Patents
A kind of cracking recovery process of n-butyl acrylate heavy constituent Download PDFInfo
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- CN110372509A CN110372509A CN201910655577.9A CN201910655577A CN110372509A CN 110372509 A CN110372509 A CN 110372509A CN 201910655577 A CN201910655577 A CN 201910655577A CN 110372509 A CN110372509 A CN 110372509A
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- C07—ORGANIC CHEMISTRY
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
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- C07C67/00—Preparation of carboxylic acid esters
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- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/317—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
- C07C67/327—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups by elimination of functional groups containing oxygen only in singly bound form
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Abstract
The invention discloses a kind of cracking recovery process of n-butyl acrylate heavy constituent, the following steps are included: in the synthesis technology for producing n-butyl acrylate as raw material using acrylic acid and n-butanol, n-butyl acrylate treating column tower bottom component is squeezed into the bottom of cracking still, acrylic acid is added in cracking still simultaneously, catalyst, polymerization inhibitor, water, it is discharged into recovery tower after cracking from the recovered overhead n-butyl acrylate of cracking still, the top of recovery tower carries out participation into esterification section after being connected to realization n-butyl acrylate heavy constituent cracking with n-butyl acrylate reaction kettle and reacts, realize recycling.The cracking recovery process of n-butyl acrylate heavy constituent of the present invention has the characteristics that the lysis efficiency height, n-butanol, the rate of recovery of n-butyl acrylate of n-butyl acrylate heavy constituent are high low with material consumption energy consumption cost.
Description
Technical field
The present invention relates to n-butyl acrylate fabricating technology field, especially a kind of n-butyl acrylate heavy constituent
Crack recovery process.
Background technique
Country's n-butyl acrylate production capacity improves year by year at present, and product yield is at being an urgent problem to be solved currently.And shadow
The principal element for ringing product yield is reactor conversion ratio, the control of selectivity and the control of the heavy constituent cracking rate of recovery.Needle
The yield of product can effectively be improved by tightening control to above-mentioned several respects, reduce the consumption of raw and auxiliary material.With acrylic acid
It is raw material with n-butanol, is produced in the production process of n-butyl acrylate by means such as reaction, extraction, rectifying, the master of generation
By-product recombination is wanted to be divided into butoxy butyl propionate (BPB), and substance Nei Ketong in heavy constituent decomposer (cracking still)
It crosses reaction and recycles part therein:
C4H9OCH2CH2COOC4H9 CH2=CHCOOC4H9 + C4H9OH
A certain amount of acrylic acid is put into cracking still to be continued esterification occurs with the butanol that is cracked to form producing acrylic acid just
Butyl ester can reach the recycling of resource.Polyacrylic acid is as one of the Main By product in propylene acid production process simultaneously,
It can also be cracked to form acrylic acid at 160 DEG C, and then reacted with n-butanol.
C4H9OH+CH2=COOH CH2=CHCOOC4H9 +H2O
C4H9OH+ C4H9OH C4H9OC4H9+H2O
But the butyl oxide (DBE) that condensation reaction generation boiling point is 142.2 DEG C of boiling point easily occurs for N-butyl under the high temperature conditions, due to
Relatively, conventional means are difficult to separate its boiling point (147.4 DEG C) with n-butyl acrylate.So in butoxy butyl propionate
In cracking process, other than improving lysis efficiency, the n-butyl acrylate rate of recovery, the generation for reducing by-product butyl oxide is also the same
It is important.
Summary of the invention
The main cracking recovery process for being designed to provide a kind of n-butyl acrylate heavy constituent of the invention, has
The lysis efficiency height of n-butyl acrylate heavy constituent, n-butanol, the rate of recovery of n-butyl acrylate are high low with material consumption energy consumption cost
The characteristics of.
The present invention can be achieved through the following technical solutions:
The invention discloses a kind of cracking recovery process of n-butyl acrylate heavy constituent, comprising the following steps: with acrylic acid
It is that raw material produces in the synthesis technology of n-butyl acrylate with n-butanol, n-butyl acrylate treating column tower bottom component is squeezed into and is split
The bottom of kettle is solved, while acrylic acid, catalyst, polymerization inhibitor, water being added in cracking still, from the recovered overhead of cracking still after cracking
N-butyl acrylate is discharged into recovery tower, and the top of recovery tower is connected to n-butyl acrylate reaction kettle is realizing acrylic acid just
Enter esterification section after the cracking of butyl ester heavy constituent and carry out participation reaction, realizes recycling；By adding simultaneously in heavy constituent cracking process
Enter a large amount of water, cracking still material viscosity both can be effectively controlled, inhibit the further polymerization of heavy component, improves butoxy propylene fourth
Ester cleavage rate and the rate of recovery；Can also reduce the blocking risk of pipeline, filter and other component, reduce maintenance of equipment rate and
Maintenance cost, energy consumption cost；In addition, water can form binary, ternary azeotropic between N-butyl, n-butyl acrylate, energy is reduced
Consumption and material consumption.Cracking still includes cracking section and exhausting section；Cracking the reaction condition of section are as follows: operation temperature is 140~180 DEG C,
Operating pressure is 75~95kpa；Exhausting section is board-like tower structure, 5~10m of tower height, 1.8~3.2m of tower diameter, the number of plates 8~15
Block.
Further, the mass content of the heavy constituent of cracking still bottom is squeezed into are as follows: n-butyl acrylate 2%~6%, butoxy
Propylene butyl ester 92%~96%, polymerization inhibitor and impurity 0.1%~2%；Polymerization inhibitor is phenthazine, in quinhydrones, hydroquinone monomethyl ether, ZJ-701
One or more kinds of mixtures.
Further, the heavy constituent feed conditions of cracking still bottom are squeezed into are as follows: 95 DEG C~115 DEG C of feeding temperature, viscosity are
10~200mPa.S, the excessively high easy aggravation heavy constituent extent of polymerization of temperature simultaneously cause viscosity to increase and crack load increase.
Further, catalyst includes that the catalyst of catalyst converter extraction tower recycling and acrylic acid preparation are mixed to form solution
Catalyst；Catalyst is one or both of methane sulfonic acid, p-methyl benzenesulfonic acid, the concentrated sulfuric acid, storng-acid cation exchange resin
Above mixture；In the catalyst of catalyst converter extraction tower recycling, catalyst content is 6%~10%, and water content is 90%~94%；
Acrylic acid preparation is mixed to form in the catalyst of solution, and catalyst content is 3%~5%.Catalyst in n-butyl acrylate synthesis
Extraction tower tower bottom recycles the investment of catalyst, can reduce the input amount of fresh catalyst, reduces cracking cost.
Further, it cracks in section and is provided with blender and bottom reboiler, increase flowing, the mixing of kettle liquid.Blender
With the use of reboiler, fully ensures that the mobility of cracking kettle liquid, prevent the aggravation of heavy constituent extent of polymerization, while also can promote
It cracks generated n-butanol and is mixed with the contact that catalyst, acrylic acid is added, improve cleavage rate, esterification yield.
Further, recycling column overhead operating pressure be 75~90KPa, tower top temperature be 85~95 DEG C, tower top material into
Enter tower top phase-splitter, aqueous portion or all reflux after condensation, oil mutually fully enters esterification section.
Further, recovery tower overhead vapours is deposited by tower top heat exchanger with the recycling catalyst aqueous solution for entering cracking still
In heat exchange.Heat exchange is carried out between recycling overhead vapours and cracking feed catalyst aqueous solution, both condensable top gaseous phase discharging,
Kettle liquid charging can also be preheated, energy consumption is reduced.Moisture content in recycling catalyst completely or partially flows back after overhead condensation, recycles
It uses, the waste water for reducing technique generates, and reduces processing cost.
Further, the acrylic acid being added in cracking still includes 0.01~20% polyacrylic acid.Polyacrylic acid is propylene
By-product in acid generation, and acrylic acid can be cracked to form under butoxy butyl propionate cracking condition and participate in reaction, make
It is of relatively low cost for the acid source in this technique.
Further.The bottom material of cracking still bottom is exported by bottomspump and carries out burning disposal.
The cracking recovery process of n-butyl acrylate heavy constituent of the present invention has following beneficial technical effect:
By the way that a large amount of water is added simultaneously in heavy constituent cracking process, cracking still material viscosity both can be effectively controlled, inhibited weight
The further polymerization of component improves butoxy propylene butyl ester cleavage rate and the rate of recovery；Can also reduce pipeline, filter and its
The blocking risk of his component reduces maintenance of equipment rate and maintenance cost, energy consumption cost；In addition, water can be with N-butyl, acrylic acid just
Binary, ternary azeotropic are formed between butyl ester, reduce energy consumption and material consumption.In production application, returned using cracking of the invention
After skill of knocking off, heavy constituent butoxy propylene butyl ester cleavage rate 87.8~91.2%, the n-butyl acrylate rate of recovery 89.2~92.4%.
Wastewater treatment capacity 7.6~10.3% can be reduced, material consumption energy consumption can reduce by 3.2~4.2%.
Detailed description of the invention
Fig. 1 is a kind of process flow chart of the cracking recovery process of n-butyl acrylate heavy constituent of the present invention；
Appended drawing reference includes: 1, first group of distributor, 2, second groups of distributors, 3, cracking still, 4, blender, 5, bottom
Material pump, 6, bottom reboiler, 7, incinerator, 8, recovery tower, 9, tower top heat exchanger, 10, catalyst recovery devices, 11, tower top
By flow container, 12, overhead reflux device, 13, reaction kettle, 14, wastewater treatment equipment.
Specific embodiment
In order that those skilled in the art will better understand the technical solution of the present invention, below with reference to embodiment and to this
Invention product is described in further detail.
As shown in Figure 1, the invention discloses a kind of cracking recovery process of n-butyl acrylate heavy constituent, including following step
It is rapid: in the synthesis technology for producing n-butyl acrylate as raw material using acrylic acid and n-butanol, to pass through first group of distributor 1
N-butyl acrylate treating column tower bottom component is squeezed into the bottom of cracking still 3, while being conveyed in cracking still 3 by the second component
Device 2 be added acrylic acid, catalyst, polymerization inhibitor, water, after cracking from the recovered overhead n-butyl acrylate of cracking still 3 be discharged into
Enter in recovery tower 8, the top of recovery tower 8 is connected to n-butyl acrylate reaction kettle 13 realizes the cracking of n-butyl acrylate heavy constituent
Participation reaction is carried out into esterification section afterwards, realizes recycling；Cracking still 3 includes cracking section and exhausting section；Crack the reaction item of section
Part are as follows: operation temperature is 140~180 DEG C, and operating pressure is 75~95kpa；Exhausting section be board-like tower structure, 5~10m of tower height,
1.8~3.2m of tower diameter, 8~15 pieces of the number of plates.
Further, the mass content of the heavy constituent of cracking still bottom is squeezed into are as follows: n-butyl acrylate 2%~6%, butoxy
Propylene butyl ester 92%~96%, polymerization inhibitor and impurity 0.1%~2%；Polymerization inhibitor is phenthazine, in quinhydrones, hydroquinone monomethyl ether, ZJ-701
One or more kinds of mixtures.
Further, the heavy constituent feed conditions of cracking still bottom are squeezed into are as follows: 95 DEG C~115 DEG C of feeding temperature, viscosity are
10~200mPa.S.
Further, catalyst includes that the catalyst of catalyst converter extraction tower recycling and acrylic acid preparation are mixed to form solution
Catalyst；Catalyst is one or both of methane sulfonic acid, p-methyl benzenesulfonic acid, the concentrated sulfuric acid, storng-acid cation exchange resin
Above mixture；In the catalyst of catalyst converter extraction tower recycling, catalyst content is 6%~10%, and water content is 90%~94%；
Acrylic acid preparation is mixed to form in the catalyst of solution, and catalyst content is 3%~5%.As shown in Figure 1, catalyst passes through catalysis
Agent recyclable device 10 is recycled.
As shown in Figure 1, being provided with blender 4 and bottom reboiler 6 in cracking section, flowing, the mixing of kettle liquid are increased.
Further, recycling column overhead operating pressure be 75~90KPa, tower top temperature be 85~95 DEG C, tower top material into
Enter tower top phase-splitter, aqueous portion or all reflux after condensation, oil mutually fully enters esterification section.
As shown in Figure 1,8 overhead vapours of recovery tower is water-soluble by tower top heat exchanger 9 and the recycling catalyst into cracking still 3
There are heat exchanges for liquid.
As shown in Figure 1, the tower top of recovery tower 8, which is equipped with tower top, is received the liquid evaporated by flow container 12, body is back to reaction
Kettle 13 is reused, and waste water is discharged to wastewater treatment equipment 14 and is handled.
Further, the acrylic acid being added in cracking still includes 0.01~20% polyacrylic acid.
As shown in Figure 1, the bottom material of 3 bottom of cracking still, which is output to incinerator 7 by bottomspump 5, carries out burning disposal.
As shown in Figure 1,
Embodiment 1
The invention discloses a kind of cracking recovery process of n-butyl acrylate heavy constituent, comprising the following steps: with acrylic acid
It is that raw material produces in the synthesis technology of n-butyl acrylate with n-butanol, n-butyl acrylate treating column tower bottom component is squeezed into and is split
The bottom of kettle is solved, while acrylic acid, catalyst, polymerization inhibitor, water being added in cracking still, from the recovered overhead of cracking still after cracking
N-butyl acrylate is discharged into recovery tower, and the top of recovery tower is connected to n-butyl acrylate reaction kettle is realizing acrylic acid just
Enter esterification section after the cracking of butyl ester heavy constituent and carry out participation reaction, realizes recycling；Cracking still includes cracking section and exhausting section；It splits
Solve the reaction condition of section are as follows: operation temperature is 180 DEG C, operating pressure 85kpa；Exhausting section is board-like tower structure, tower height 5m, tower
Diameter 3.2m, 12 pieces of the number of plates.
In the present embodiment, the heavy constituent content of cracking still bottom is squeezed into are as follows: n-butyl acrylate 2%, butoxy propylene fourth
Ester 96%, polymerization inhibitor and impurity 2%, polymerization inhibitor are phenthazine；Feed conditions are as follows: 115 DEG C of feeding temperature, viscosity 105mPa.S.
In the present embodiment, catalyst include catalyst converter extraction tower recycling catalyst and acrylic acid preparation be mixed to form it is molten
The catalyst of liquid；In the catalyst of catalyst converter extraction tower recycling, catalyst is methane sulfonic acid；Catalyst content is 6%, water content
It is 94%；Acrylic acid preparation is mixed to form in the catalyst of solution, catalyst content 5%.
In the present embodiment, it cracks in section and is provided with blender and bottom reboiler, increase flowing, the mixing of kettle liquid.
In the present embodiment, recycling column overhead operating pressure is 90KPa, and tower top temperature is 90 DEG C, and tower top material is into condensation
Enter tower top phase-splitter, aqueous portion or all reflux afterwards, oil mutually fully enters esterification section.Recovery tower overhead vapours passes through tower top
There are heat exchanges with the recycling catalyst aqueous solution into cracking still for heat exchanger.
In the present embodiment, the acrylic acid being added in cracking still includes 20% polyacrylic acid.
The bottom material of cracking still bottom is exported by bottomspump and carries out burning disposal.
Embodiment 2
The invention discloses a kind of cracking recovery process of n-butyl acrylate heavy constituent, comprising the following steps: with acrylic acid
It is that raw material produces in the synthesis technology of n-butyl acrylate with n-butanol, n-butyl acrylate treating column tower bottom component is squeezed into and is split
The bottom of kettle is solved, while acrylic acid, catalyst, polymerization inhibitor, water being added in cracking still, from the recovered overhead of cracking still after cracking
N-butyl acrylate is discharged into recovery tower, and the top of recovery tower is connected to n-butyl acrylate reaction kettle is realizing acrylic acid just
Enter esterification section after the cracking of butyl ester heavy constituent and carry out participation reaction, realizes recycling；Cracking still includes cracking section and exhausting section；It splits
Solve the reaction condition of section are as follows: operation temperature is 160 DEG C, operating pressure 75kpa；Exhausting section be board-like tower structure, tower height 10m,
Tower diameter 2.5m, 8 pieces of the number of plates.
In the present embodiment, the heavy constituent content of cracking still bottom is squeezed into are as follows: n-butyl acrylate 6%, butoxy propylene fourth
Ester 92%, polymerization inhibitor and impurity 2%, polymerization inhibitor are quinhydrones；Feed conditions are as follows: 105 DEG C of feeding temperature, viscosity 10mPa.S.
In the present embodiment, catalyst include catalyst converter extraction tower recycling catalyst and acrylic acid preparation be mixed to form it is molten
The catalyst of liquid；Catalyst is p-methyl benzenesulfonic acid；In the catalyst of catalyst converter extraction tower recycling, catalyst content 8%, water contains
Amount is 92%；Acrylic acid preparation is mixed to form in the catalyst of solution, catalyst content 4%.
In the present embodiment, it cracks in section and is provided with blender and bottom reboiler, increase flowing, the mixing of kettle liquid.
In the present embodiment, recycling column overhead operating pressure is 85KPa, and tower top temperature is 85 DEG C, and tower top material is into condensation
Enter tower top phase-splitter, aqueous portion or all reflux afterwards, oil mutually fully enters esterification section.Recovery tower overhead vapours passes through tower top
There are heat exchanges with the recycling catalyst aqueous solution into cracking still for heat exchanger.
In the present embodiment, the acrylic acid being added in cracking still includes 10% polyacrylic acid.
The bottom material of cracking still bottom is exported by bottomspump and carries out burning disposal.
Embodiment 3
The invention discloses a kind of cracking recovery process of n-butyl acrylate heavy constituent, comprising the following steps: with acrylic acid
It is that raw material produces in the synthesis technology of n-butyl acrylate with n-butanol, n-butyl acrylate treating column tower bottom component is squeezed into and is split
The bottom of kettle is solved, while acrylic acid, catalyst, polymerization inhibitor, water being added in cracking still, from the recovered overhead of cracking still after cracking
N-butyl acrylate is discharged into recovery tower, and the top of recovery tower is connected to n-butyl acrylate reaction kettle is realizing acrylic acid just
Enter esterification section after the cracking of butyl ester heavy constituent and carry out participation reaction, realizes recycling；Cracking still includes cracking section and exhausting section；It splits
Solve the reaction condition of section are as follows: operation temperature is 140 DEG C, operating pressure 95kpa；Exhausting section is board-like tower structure, tower height 8m, tower
Diameter 1.8m, 15 pieces of the number of plates.
In the present embodiment, the heavy constituent content of cracking still bottom is squeezed into are as follows: n-butyl acrylate 4%, butoxy propylene fourth
Ester 95%, polymerization inhibitor and impurity 1%, polymerization inhibitor are hydroquinone monomethyl ether；Feed conditions are as follows: 95 DEG C of feeding temperature, viscosity are
200mPa.S。
In the present embodiment, catalyst include catalyst converter extraction tower recycling catalyst and acrylic acid preparation be mixed to form it is molten
The catalyst of liquid；Catalyst is the concentrated sulfuric acid；In the catalyst of catalyst converter extraction tower recycling, catalyst content 8%, water content is
92%；Acrylic acid preparation is mixed to form in the catalyst of solution, catalyst content 3%.
In the present embodiment, it cracks in section and is provided with blender and bottom reboiler, increase flowing, the mixing of kettle liquid.
In the present embodiment, recycling column overhead operating pressure is 75KPa, and tower top temperature is 95 DEG C, and tower top material is into condensation
Enter tower top phase-splitter, aqueous portion or all reflux afterwards, oil mutually fully enters esterification section.Recovery tower overhead vapours passes through tower top
There are heat exchanges with the recycling catalyst aqueous solution into cracking still for heat exchanger.
In the present embodiment, the acrylic acid being added in cracking still includes 0.01% polyacrylic acid.
The bottom material of cracking still bottom is exported by bottomspump and carries out burning disposal.
Embodiment 4
The invention discloses a kind of cracking recovery process of n-butyl acrylate heavy constituent, comprising the following steps: with acrylic acid
It is that raw material produces in the synthesis technology of n-butyl acrylate with n-butanol, n-butyl acrylate treating column tower bottom component is squeezed into and is split
The bottom of kettle is solved, while acrylic acid, catalyst, polymerization inhibitor, water being added in cracking still, from the recovered overhead of cracking still after cracking
N-butyl acrylate is discharged into recovery tower, and the top of recovery tower is connected to n-butyl acrylate reaction kettle is realizing acrylic acid just
Enter esterification section after the cracking of butyl ester heavy constituent and carry out participation reaction, realizes recycling；Cracking still includes cracking section and exhausting section；It splits
Solve the reaction condition of section are as follows: operation temperature is 150 DEG C, operating pressure 80kpa；Exhausting section is board-like tower structure, tower height 9m, tower
Diameter 2m, 10 pieces of the number of plates.
In the present embodiment, the heavy constituent content of cracking still bottom is squeezed into are as follows: n-butyl acrylate 3%, butoxy propylene fourth
Ester 95.5%, polymerization inhibitor and impurity 1.5%, polymerization inhibitor ZJ-701；Feed conditions are as follows: 100 DEG C of feeding temperature, viscosity are
60mPa.S。
In the present embodiment, catalyst include catalyst converter extraction tower recycling catalyst and acrylic acid preparation be mixed to form it is molten
The catalyst of liquid；Catalyst is methane sulfonic acid, p-methyl benzenesulfonic acid, storng-acid cation exchange resin；The recycling of catalyst converter extraction tower
Catalyst in, catalyst content 9%, water content 91%；Acrylic acid preparation is mixed to form in the catalyst of solution, catalyst
Content is 5%.
In the present embodiment, it cracks in section and is provided with blender and bottom reboiler, increase flowing, the mixing of kettle liquid.
In the present embodiment, recycling column overhead operating pressure is 80KPa, and tower top temperature is 91 DEG C, and tower top material is into condensation
Enter tower top phase-splitter, aqueous portion or all reflux afterwards, oil mutually fully enters esterification section.Recovery tower overhead vapours passes through tower top
There are heat exchanges with the recycling catalyst aqueous solution into cracking still for heat exchanger.
In the present embodiment, the acrylic acid being added in cracking still includes 2% polyacrylic acid.
The bottom material of cracking still bottom is exported by bottomspump and carries out burning disposal.
Embodiment 5
The invention discloses a kind of cracking recovery process of n-butyl acrylate heavy constituent, comprising the following steps: with acrylic acid
It is that raw material produces in the synthesis technology of n-butyl acrylate with n-butanol, n-butyl acrylate treating column tower bottom component is squeezed into and is split
The bottom of kettle is solved, while acrylic acid, catalyst, polymerization inhibitor, water being added in cracking still, from the recovered overhead of cracking still after cracking
N-butyl acrylate is discharged into recovery tower, and the top of recovery tower is connected to n-butyl acrylate reaction kettle is realizing acrylic acid just
Enter esterification section after the cracking of butyl ester heavy constituent and carry out participation reaction, realizes recycling；Cracking still includes cracking section and exhausting section；It splits
Solve the reaction condition of section are as follows: operation temperature is 170 DEG C, operating pressure 88kpa；Exhausting section is board-like tower structure, tower height 9m, tower
Diameter 2.8m, 13 pieces of the number of plates.
In the present embodiment, the heavy constituent content of cracking still bottom is squeezed into are as follows: n-butyl acrylate 5%, butoxy propylene fourth
Ester 94%, polymerization inhibitor and impurity 1%, polymerization inhibitor are phenthazine, quinhydrones, hydroquinone monomethyl ether, ZJ-701；Feed conditions are as follows: charging temperature
Spend 110 DEG C, viscosity 80mPa.S.
In the present embodiment, catalyst include catalyst converter extraction tower recycling catalyst and acrylic acid preparation be mixed to form it is molten
The catalyst of liquid；Catalyst is methane sulfonic acid, p-methyl benzenesulfonic acid；In the catalyst of catalyst converter extraction tower recycling, catalyst content
It is 9%, water content 91%；Acrylic acid preparation is mixed to form in the catalyst of solution, catalyst content 3.5%.
In the present embodiment, it cracks in section and is provided with blender and bottom reboiler, increase flowing, the mixing of kettle liquid.
In the present embodiment, recycling column overhead operating pressure is 780KPa, and tower top temperature is 88 DEG C, and tower top material is into condensation
Enter tower top phase-splitter, aqueous portion or all reflux afterwards, oil mutually fully enters esterification section.Recovery tower overhead vapours passes through tower top
There are heat exchanges with the recycling catalyst aqueous solution into cracking still for heat exchanger.
In the present embodiment,
The bottom material of cracking still bottom is exported by bottomspump and carries out burning disposal.
Application Example 1
The invention discloses a kind of cracking recovery process of n-butyl acrylate heavy constituent, constituent content is n-butyl acrylate
4.2%, butoxy butyl propionate 94.5%, polymerization inhibitor 0.7%, impurity 0.6% heavy constituent (25 mPa.S of viscosity) pumped with 400kg/h
Enter cracking still bottom, 120kg/h recycle catalyst aqueous solution (catalyst content 8.5%) with enter after overhead vapours heat exchange
Cracking still bottom, while containing polyacrylic acid 12%, acrylic acid 88%(catalyst content 1.8%) with 180kg/h.Control cracking still kettle
160 DEG C, pressure 84kpa of temperature, 85 DEG C of tower top drop temperature, load 630kg/h, content is n-butyl acrylate 72.2%, positive fourth
Alcohol 13.6%, acrylic acid 2.3%, water 10% and a small amount of impurity, the water phase infinite reflux after condensing.Heavy constituent butoxy propylene butyl ester
Cleavage rate 88.3%, the n-butyl acrylate rate of recovery 90.2% can reduce wastewater treatment capacity 8.2%, and material consumption energy consumption can reduce by 3.5%.
Application Example 2
The invention discloses a kind of cracking recovery process of n-butyl acrylate heavy constituent, constituent content is n-butyl acrylate
5.0%, butoxy butyl propionate 93.5%, polymerization inhibitor 0.8%, impurity 0.7% heavy constituent (20 mPa.S of viscosity) pumped with 380kg/h
Enter cracking still bottom, 100kg/h recycle catalyst aqueous solution (catalyst content 9.3%) with enter after overhead vapours heat exchange
Cracking still bottom, while containing polyacrylic acid 15%, acrylic acid 90%(catalyst content 1.2%) with 160kg/h.Control cracking still kettle
155 DEG C, pressure 88kpa of temperature, 83 DEG C of tower top drop temperature, load 565kg/h, content is n-butyl acrylate 74.0%, positive fourth
Alcohol 11.3%, acrylic acid 2.1%, water 9.8% and a small amount of impurity, the water phase infinite reflux after condensing.Heavy constituent butoxy propylene butyl ester
Cleavage rate 91.2%, the n-butyl acrylate rate of recovery 92.4% can reduce wastewater treatment capacity 7.6%, and material consumption energy consumption can reduce by 3.2%.
Application Example 3
The invention discloses a kind of cracking recovery process of n-butyl acrylate heavy constituent, constituent content is n-butyl acrylate
6%, butoxy butyl propionate 92.1%, polymerization inhibitor 0.8%, impurity 1.1% heavy constituent (18 mPa.S of viscosity) be pumped into 450kg/h
Cracking still bottom, 150kg/h recycle catalyst aqueous solution (catalyst content 8.9%) with after overhead vapours heat exchange enter split
Bottom portion is solved, fresh propylene acid (catalyst content 1.5%) additional amount is 250kg/h.172 DEG C of cracking still kettle temperature of control, pressure
95kpa, 82 DEG C of tower top drop temperature, load 770kg/h, content is n-butyl acrylate 70.6%, n-butanol 12.8%, propylene
Acid 3.5%, water 12.1% and a small amount of impurity, the water phase infinite reflux after condensing.Heavy constituent butoxy propylene butyl ester cleavage rate
87.8%, the n-butyl acrylate rate of recovery 89.2%.Wastewater treatment capacity 10.3% can be reduced, material consumption energy consumption can reduce by 4.2%.
More than, only presently preferred embodiments of the present invention is not intended to limit the present invention in any form；All current rows
The those of ordinary skill of industry can be shown in by specification and above and swimmingly implement the present invention；But all it is familiar with this profession
Technical staff without departing from the scope of the present invention, made using disclosed above technology contents it is a little more
Dynamic, modification and the equivalent variations developed, are equivalent embodiment of the invention；Meanwhile all substantial technologicals pair according to the present invention
The variation, modification and evolution etc. of any equivalent variations made by above embodiments, still fall within the guarantor of technical solution of the present invention
Within the scope of shield.
Claims (9)
1. a kind of cracking recovery process of n-butyl acrylate heavy constituent, it is characterised in that the following steps are included:
In the synthesis technology for producing n-butyl acrylate as raw material using acrylic acid and n-butanol, by n-butyl acrylate treating column
Tower bottom component squeezes into the bottom of cracking still, while acrylic acid, catalyst, polymerization inhibitor, water being added in cracking still, from splitting after cracking
The recovered overhead n-butyl acrylate of solution kettle is discharged into recovery tower, and the top of recovery tower and n-butyl acrylate reaction kettle connect
Enter esterification section after logical realization n-butyl acrylate heavy constituent cracking and carry out participation reaction, realizes and recycle；
The cracking still includes cracking section and exhausting section；
The reaction condition of the cracking section are as follows: operation temperature is 140~180 DEG C, and operating pressure is 75~95kpa；
The exhausting section be board-like tower structure, 5~10m of tower height, 1.8~3.2m of tower diameter, 8~15 pieces of the number of plates.
2. the cracking recovery process of n-butyl acrylate heavy constituent according to claim 1, it is characterised in that: squeeze into cracking
Respectively formed in the heavy constituent in bottom portion mass content be respectively as follows: n-butyl acrylate 2%~6%, butoxy propylene butyl ester 92%~
96%, polymerization inhibitor and impurity 0.1%~2%, the polymerization inhibitor be one of phenthazine, quinhydrones, hydroquinone monomethyl ether, ZJ-701 or
Two or more mixtures.
3. the cracking recovery process of n-butyl acrylate heavy constituent according to claim 1 or 2, it is characterised in that: squeeze into
The heavy constituent feed conditions of cracking still bottom are as follows: 95 DEG C~115 DEG C of feeding temperature, viscosity are 10~200mPa.S.
4. the cracking recovery process of n-butyl acrylate heavy constituent according to claim 3, it is characterised in that: the catalysis
Agent includes that the catalyst of catalyst converter extraction tower recycling and acrylic acid prepare the catalyst for being mixed to form solution；
Catalyst is one or more of methane sulfonic acid, p-methyl benzenesulfonic acid, the concentrated sulfuric acid, storng-acid cation exchange resin
Mixture；
In the catalyst of catalyst converter extraction tower recycling, catalyst content is 6%~10%, and water content is 90%~94%；
Acrylic acid preparation is mixed to form in the catalyst of solution, and catalyst content is 3%~5%.
5. the cracking recovery process of n-butyl acrylate heavy constituent according to claim 4, it is characterised in that: the cracking
It is provided with blender and bottom reboiler in section, increases flowing, the mixing of kettle liquid.
6. the cracking recovery process of n-butyl acrylate heavy constituent according to claim 5, it is characterised in that: recovery tower tower
Top operating pressure is 75~90KPa, and tower top temperature is 85~95 DEG C, and tower top material is into entering tower top phase-splitter, water phase after condensation
Partly or entirely reflux, oil mutually fully enter esterification section.
7. the cracking recovery process of n-butyl acrylate heavy constituent according to claim 6, it is characterised in that: recovery tower tower
Pushing up steam, there are heat exchanges with the recycling catalyst aqueous solution into cracking still by tower top heat exchanger.
8. the cracking recovery process of n-butyl acrylate heavy constituent according to claim 7, it is characterised in that: cracking is added
Acrylic acid in kettle includes 0.01~20% polyacrylic acid.
9. the cracking recovery process of n-butyl acrylate heavy constituent according to claim 8, it is characterised in that: the cracking
The bottom material in bottom portion is exported by bottomspump and carries out burning disposal.
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