CN106397182A - Polymerization inhibitor for preparation apparatus of acrylic acid - Google Patents
Polymerization inhibitor for preparation apparatus of acrylic acid Download PDFInfo
- Publication number
- CN106397182A CN106397182A CN201610799034.0A CN201610799034A CN106397182A CN 106397182 A CN106397182 A CN 106397182A CN 201610799034 A CN201610799034 A CN 201610799034A CN 106397182 A CN106397182 A CN 106397182A
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- Prior art keywords
- polymerization inhibitor
- acrylic acid
- acetic acid
- polymerization
- tower
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/50—Use of additives, e.g. for stabilisation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a polymerization inhibitor for a preparation apparatus of acrylic acid. The polymerization inhibitor contains 2,6-dimethylpiperidin-1-oxyl free radical and N,N'-dimethylthiourea, the mass ratio is 1:1-1.5, and the polymerization inhibitor is applied to a C2 acetic acid removing tower and/or a C2 return tank of the preparation apparatus of acrylic acid. The polymerization inhibitor is an environmental protection high-efficient polymerization inhibitor, and the polymerization inhibitor has the advantages of few usage amounts without toxicity and generation of corrosion; good polymerization inhibiting effects are provided, environment and occupational health of employees are protected, and the polymerization inhibitor accords with high efficient and environmentally friendly production and operation ideas.
Description
Technical field
The present invention relates to acrylic acid preparing technical field, especially relate to one kind and prepare resistance used in acrylic acid device
Poly- agent.
Background technology
Acrylicacidandesters belong to the vinyl monomer of easily polymerization, generally existing polymerism in its production process,
For the reaction generating oligomer, suitable measures can be taken to be suppressed within the acceptable range；The phenomenons such as vinyl polymerization
Generation, its result can generate that relative molecular mass is big, highly insoluble, outward appearance is in puffed rice or elastomeric end poly polymer,
These polymer plugging pipeline, column plate, pump housings, the stable operation to technique and process units causes large effect.Therefore, must
Rational measure must be taken to avoid the occurrence of this, at present modal method be exactly add in process of production suitable
Polymerization inhibitor.
Main polymerization inhibitor in producing currently used for acrylicacidandesters divides two classes：One class is chain tra nsfer type, mainly has hydrogen
Quinone (HQ), hydroquinone monomethyl ether (MQ), phenothiazine (PZ) etc.；Another kind of for metal salt form, mainly have cupric acetate (AI-61A), two fourths
Base aminodithioformic acid copper (AI-61R) etc..In addition, free radical type polymerization inhibitor such as piperidine NO free radical (701,705) also exists
Applied in partial devices.Use for polymerization inhibitor situation with regard to current acrylic monomer process units, except known HQ
Have outside synergism with PZ, remaining has synergistic compound polymerization inhibitor seldom, is reported according to nearest domestic and foreign literature,
Reach efficient purpose on a small quantity using composite polymerzation inhibitor and become major trend.
Magazine is published according to German H.Vogel《Chemical Engineering&Technology》(title：
Phenothiazine as Stabilizer for Acrylic Acid) on result of study, polymerization inhibitor is in acrylic acid
Consumption wayses have three kinds：The thermal decomposition when reaction with free radical, dissolved oxygen oxidation or high temperature.
The mode being consumed in different operation stage polymerization inhibitors also has difference：More than 90 DEG C, polymerization inhibitor is dissolved oxygen oxygen
Change is topmost consumption wayses, and less than 90 DEG C radical reactions are main consumption wayses.Just meeting when only more than 90 DEG C
Have more than 10% polymerization inhibitor thermal decomposition consume.In the high-temperature technology stage, it is main that polymerization inhibitor is dissolved oxygen oxidation
Consumption wayses, be used resistant to elevated temperatures PZ as main polymerization inhibitor and a small amount of mantoquita as free radical scavenger, this stage is basic
All plant composite polymerzation inhibitor, using being so substantially not changed in for many years；In the temperature relatively low stage, radical reaction is that polymerization inhibitor is main
Consumption wayses, dissolved oxygen oxidation is deputy consumption wayses it should use resistant to elevated temperatures PZ and chain tra nsfer type polymerization inhibitor such as
The composite polymerzation inhibitors such as HQ, PZ and HQ composite polymerzation inhibitor.
Conventional polymerization inhibitor has AI-61A, PZ, MQ, HQ, AI-61R, chain tra nsfer type polymerization inhibitor HQ, MQ etc. general and other
Polymerization inhibitor compounding effect more preferably, but under conditions of aerobic and anaerobic, polymerization inhibition effect difference is very big, PZ, HQ, usage amount is larger,
Cost is also higher.More and more new polymerization inhibitor is used in recent years.
Content of the invention
The problems referred to above existing for prior art, the applicant provides a kind of resistance for preparing acrylic acid device
Poly- agent.The polymerization inhibitor WX-901 that the inventive method provides is a kind of high-efficiency polymerization inhibitor of environment-friendly type, and avirulence does not produce burn into
Consumption is less, while obtaining more preferable polymerization inhibition effect, protects environment and employee's occupational health again, meets efficient, environmental protection
Production and operation theory.
Technical scheme is as follows：
A kind of polymerization inhibitor for preparing acrylic acid device, described polymerization inhibitor contains 2,6- lupetidine -1- epoxide
Free radical and N, N- dimethyl sulfourea, and both mass ratioes are 1:1～1.5.
A kind of application of described polymerization inhibitor, by described polymerization inhibitor add prepare acrylic acid device C2 take off acetic acid tower with/
Or in C2 return tank.
Described polymerization inhibitor is dissolved in organic solvent, takes off acetic acid tower by needle cylinder injection type or dosing pump pouring-in addition C2
And/or in C2 return tank.
The consumption of described polymerization inhibitor takes off 0.03～0.04wt% of crude acrylic acid amount in acetic acid tower for C2.
Beneficial the having technical effect that of the present invention：
1) free radical in polymerization inhibitor WX-901 in the inventive method can effectively suppress the radical polymerization of olefinic monomer,
Stop the generation of single, double olefin fraction poly oxide and the blocking of the pipeline thus causing and equipment.
2) in the inventive method polymerization inhibitor WX-901 in coupling reaction and dismutation reaction all as radical-scavenging body, no
But do not produce living chain with monomer moreover it is possible to quickly and effectively catch the free radical on living chain, thus playing inhibition, stable
Property than traditional polymerization inhibitor reaction generate Sequence of Relative Stability of Free Radicals high.
3) free radical in polymerization inhibitor WX-901 in the inventive method, is a kind of high mars free radical of stable state, once running into
Polymerization or due to heat with produced by oxygen during various free radical R or ROO etc., in connection rapidly become stable molecule,
Eliminate the various free radicals that reaction produces, thoroughly suppress being normally carried out of polyreaction；And free radical exists in WX-901
Lone pair electrons produce delocalization effect between nitrogen-oxygen bond makes it highly stable, can preserve for a long time and never degenerate.
Brief description
Fig. 1 is prepared the schematic diagram of acrylic acid device for the present invention by crude acrylic acid purification.
Specific embodiment
With reference to the accompanying drawings and examples, the present invention is specifically described.
Fig. 1 is to prepare acrylic acid device, and it is plate column that wherein C2 takes off acetic acid tower, inside has 37 blocks of turbogrid trays；Crude acrylic acid
Enter C2 to take off in acetic acid tower, wherein acetic acid, water, toluene, acrylic acid steam from C2 tower top together through rectification under vacuum, steaming thing is through the
One condenser is flowed into C2 return tank by CTW (recirculated water) partial condensation, condensed fluid, does not coagulate gas and enters the second condenser by CWA
(5 DEG C of chilled waters) condenses further, and condensed fluid also flows into C2 return tank；Liquid in C2 return tank is pumped out by C2 backflow, and one
Road enters in tower from C2 overhead reflux as backflow；The liquid level controlling C2 return tank is sent out on another road as discharging, through place
Reason, final C2 takes off only remaining acrylic acid and part heavy constituent in acetic acid tower；Crude acrylic acid enters back into refined after the de- acetic acid of C2
Tower is obtained industrial acrylic acid.
Embodiment 1
A kind of polymerization inhibitor for preparing acrylic acid device, described polymerization inhibitor contains 2,6- lupetidine -1- epoxide
Free radical and N, N- dimethyl sulfourea, and both mass ratioes are 1:1.
A kind of application of described polymerization inhibitor, described polymerization inhibitor is added the C2 preparing acrylic acid device take off acetic acid tower
(4KPaA、90℃)；Wherein polymerization inhibitor consumption takes off the 0.03wt% of crude acrylic acid in acetic acid tower for C2.Joined by polymerization inhibitor of the present invention
Purity of acrylic acid product >=99.5%, colourity ＜ 10 with preparation.
Embodiment 2
A kind of polymerization inhibitor for preparing acrylic acid device, described polymerization inhibitor contains 2,6- lupetidine -1- epoxide
Free radical and N, N- dimethyl sulfourea, and both mass ratioes are 1:1.5.
A kind of application of described polymerization inhibitor, described polymerization inhibitor is added the C2 preparing acrylic acid device take off acetic acid tower
In (4KPaA, 90 DEG C) and C2 return tank；Wherein polymerization inhibitor consumption takes off acetic acid tower (4KPaA, 90 DEG C) and wherein polymerization inhibitor use for C2
Measure the 0.04wt% taking off crude acrylic acid in acetic acid tower for C2.The purity of acrylic acid product prepared by polymerization inhibitor of the present invention participation >=
99.5%th, colourity ＜ 10.
Embodiment 3
A kind of polymerization inhibitor for preparing acrylic acid device, described polymerization inhibitor contains 2,6- lupetidine -1- epoxide
Free radical and N, N- dimethyl sulfourea, and both mass ratioes are 1:1.
A kind of application of described polymerization inhibitor, described polymerization inhibitor is dissolved in organic solvent and enters to prepare acrylic acid by needle cylinder injection
The C2 of device take off in acetic acid tower (4KPaA, 90 DEG C).The consumption of described polymerization inhibitor takes off crude acrylic acid amount in acetic acid tower for C2
0.04wt%.Purity of acrylic acid product >=99.5% of preparation is participated in by polymerization inhibitor of the present invention, colourity is 8.
Test case：
WX-901 heats to commercially available industry acrylic acid in laboratory under the conditions of C2 takes off acetic acid tower (4KPaA, 90 DEG C)
Polymerization experiment, test result is as shown in table 1 below：
Table 1
Test from above：
(1) use HQ, PZ mixing polymerization inhibitor, polymerization time is 19min；(2) WX-901 is used to replace HQ, polymerization time is
21min；(3) WX-901 is used to replace HQ and PZ, polymerization time is 21min；Therefore, replaced now using less WX-901 polymerization inhibitor
There is HQ, PZ compound polymerization inhibitor that device uses, the WX-901 of 60ppm can reach the polymerization inhibition effect using the former polymerization inhibitor of 300ppm,
Polymerization inhibitor polymerization inhibition effect of the present invention more preferably, and economizes in raw materials；Existing 60,000 tons of devices of chemical industry use, originally daily using PZ
180kg, HQ 120kg, is first replaced using the WX-901 of 60kg, plant running is normal, runs and is not affected by affecting, the making of polymerization inhibitor
It is reduced to 6000 yuan/ton with cost by original 10500 yuan/ton, and acrylic acid physicochemical property is obtained and can reach high-class product
More than：Product purity >=99.5%, colourity≤10.
Claims (4)
1. a kind of polymerization inhibitor for preparing acrylic acid device is it is characterised in that described polymerization inhibitor contains 2,6- dimethyl piperazine
Pyridine -1- epoxide free radical and N, N- dimethyl sulfourea, and both mass ratioes are 1:1～1.5.
2. a kind of application of the polymerization inhibitor described in claim 1 it is characterised in that prepare acrylic acid by the addition of described polymerization inhibitor
The C2 of device takes off in acetic acid tower and/or C2 return tank.
3. application according to claim 2 is it is characterised in that described polymerization inhibitor is dissolved in organic solvent, by needle cylinder injection
Formula or dosing pump pouring-in addition C2 take off in acetic acid tower and/or C2 return tank.
4. application according to claim 2 is it is characterised in that the consumption of described polymerization inhibitor takes off crude propylene in acetic acid tower for C2
0.03～0.04wt% of acid amount.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610799034.0A CN106397182A (en) | 2016-08-31 | 2016-08-31 | Polymerization inhibitor for preparation apparatus of acrylic acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610799034.0A CN106397182A (en) | 2016-08-31 | 2016-08-31 | Polymerization inhibitor for preparation apparatus of acrylic acid |
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| Publication Number | Publication Date |
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| CN106397182A true CN106397182A (en) | 2017-02-15 |
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| CN201610799034.0A Pending CN106397182A (en) | 2016-08-31 | 2016-08-31 | Polymerization inhibitor for preparation apparatus of acrylic acid |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106905188A (en) * | 2017-02-24 | 2017-06-30 | 北京誉天利化工有限公司 | A kind of polymerization inhibitor and its application in production device for acrylic nitrile |
| CN114656353A (en) * | 2022-04-13 | 2022-06-24 | 卫星化学股份有限公司 | Application of green environment-friendly compound in production process of acrylic acid |
| CN115322273A (en) * | 2022-08-04 | 2022-11-11 | 万华化学集团股份有限公司 | Polymerization inhibitor and application thereof in synthesis of isobornyl (meth) acrylate |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86103840A (en) * | 1986-06-05 | 1987-12-16 | 化学工业部锦西化工研究院 | The composite polymerzation inhibitor of methacrylic acid and ester class thereof |
| CN1270952A (en) * | 1999-03-31 | 2000-10-25 | 株式会社日本触媒 | Refining method for (methyl) acrylic acid |
| CN101910105A (en) * | 2007-12-27 | 2010-12-08 | 株式会社日本触媒 | Alpha-hydroxymethyl acrylate compounds and method of producing the same |
| CN103467230A (en) * | 2013-07-24 | 2013-12-25 | 金浦新材料股份有限公司 | Water-soluble styrene polymerization inhibitor |
| CN103848735A (en) * | 2014-01-16 | 2014-06-11 | 中国石油集团东北炼化工程有限公司吉林设计院 | Application of composite polymerization inhibitors in crylic acid refining process |
-
2016
- 2016-08-31 CN CN201610799034.0A patent/CN106397182A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86103840A (en) * | 1986-06-05 | 1987-12-16 | 化学工业部锦西化工研究院 | The composite polymerzation inhibitor of methacrylic acid and ester class thereof |
| CN1270952A (en) * | 1999-03-31 | 2000-10-25 | 株式会社日本触媒 | Refining method for (methyl) acrylic acid |
| CN101910105A (en) * | 2007-12-27 | 2010-12-08 | 株式会社日本触媒 | Alpha-hydroxymethyl acrylate compounds and method of producing the same |
| CN103467230A (en) * | 2013-07-24 | 2013-12-25 | 金浦新材料股份有限公司 | Water-soluble styrene polymerization inhibitor |
| CN103848735A (en) * | 2014-01-16 | 2014-06-11 | 中国石油集团东北炼化工程有限公司吉林设计院 | Application of composite polymerization inhibitors in crylic acid refining process |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106905188A (en) * | 2017-02-24 | 2017-06-30 | 北京誉天利化工有限公司 | A kind of polymerization inhibitor and its application in production device for acrylic nitrile |
| CN114656353A (en) * | 2022-04-13 | 2022-06-24 | 卫星化学股份有限公司 | Application of green environment-friendly compound in production process of acrylic acid |
| CN115322273A (en) * | 2022-08-04 | 2022-11-11 | 万华化学集团股份有限公司 | Polymerization inhibitor and application thereof in synthesis of isobornyl (meth) acrylate |
| CN115322273B (en) * | 2022-08-04 | 2023-05-30 | 万华化学集团股份有限公司 | Polymerization inhibitor and application thereof in synthesis of isobornyl (meth) acrylate |
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Application publication date: 20170215 |