CN102464555A - Polymerization inhibitor used in thermal dimerization process of petroleum cracking C5 fraction - Google Patents

Polymerization inhibitor used in thermal dimerization process of petroleum cracking C5 fraction Download PDF

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CN102464555A
CN102464555A CN201010535960XA CN201010535960A CN102464555A CN 102464555 A CN102464555 A CN 102464555A CN 201010535960X A CN201010535960X A CN 201010535960XA CN 201010535960 A CN201010535960 A CN 201010535960A CN 102464555 A CN102464555 A CN 102464555A
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octanol
stopper
ortho
dmko
polymerization inhibitor
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CN201010535960XA
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Chinese (zh)
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CN102464555B (en
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任海伦
程延华
高玉玲
韩小平
金允子
李丽萍
陈万友
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中国石油天然气股份有限公司
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Abstract

The invention relates to a polymerization inhibitor used in the thermal dimerization process of petroleum cracking C5 fraction. The polymerization inhibitor is composed of dimethyl ketoxime, octanol and ortho amino phenolic acid. The weight ratio of dimethyl ketoxime to octanol to ortho amino phenolic acid is 1:0.01-10.0:0.1-12.0. The content of dimethyl ketoxime, octanol and ortho amino phenolic acid in a solvent is 1-20wt%. The amount of the polymerization inhibitor in the petroleum cracking C5 fraction is 50-1200ppm. The polymerization inhibitor has a good polymerization inhibition effect, and can be used to effectively inhibit self-polymerization or copolymerization of diolefin in the petroleum cracking C5 fraction in a reactor or a separation tower, so as to avoid obstruction of a preheater or a reboiler, prolong stable operation period of a device and effectively reduce the loss rate of isoprene. The polymerization inhibitor has advantages of less amount and low cost, and is easy to separate.

Description

A kind of stopper that is used for the hot dimerization of five fractions of petroleum cracked carbon

Technical field

The present invention relates to a kind of five fractions of petroleum cracked carbon polymeric stopper that is used to suppress, particularly the hot dimerization of five fractions of petroleum cracked carbon suppresses the stopper of olefinic polymerization.

Background technology

C5 fraction (its classical group prejudice table 1) is the by product of petroleum cracking system ethene, generally is about 10%~20% of ethylene yield.China's carbon five resources never obtain good use, have only few part to be used to produce common C 5 petroleum resin, or carry out simple separation and produce NSC 7352 (DCPD), and major part acts as a fuel and burns, and causes significant wastage.If the component in the C5 fraction is separated, produce the Chemicals of a series of high added values through them, can reduce production cost of ethylene greatly, improve economic benefit of enterprises and competitive power.

At present, carbon five separates and utilizes cyclopentadiene (CPD) to be easy to the characteristics that autohemagglutination becomes DCPD mostly, at first, with the hot dimerization of carbon slender acanthopanax, remove DCPD and other heavy constituent after, separating isoprene (IP) and m-pentadiene (PD) from light constituent again.Because component is many in the cracking c_5, cause hot dimerization reaction process very complicated, CPD is easy to dimerization and generates DCPD, also can generate dipolymer with IP or PD copolymerization simultaneously, causes IP and PD loss, is mixed with a large amount of multipolymers among the DCPD that obtains simultaneously, makes its content lower.

In the hot dimerization of C5 fraction, generally adopt pressurized operation, the renders operation temperature is higher; And diolefin character is very active, and the higher or easy polymerization reaction take place when contacting with oxide compound in temperature is when diolefin concentration is higher; Be prone to generate polymkeric substance, after the formation polymerization site, the molecular weight of polymkeric substance increases gradually; Its mobile variation; Finally make line clogging and reactor wall gum deposit, cause loss of monomer, energy consumption increase, heat exchange weak effect, must clean reactor drum, pre-heating system and pipeline when serious comprehensively.

In the hot dimerization of C5 fraction, the yield of NSC 7352 and the rate of loss of isoprene are to investigate the important indicator of hot dimerization processes.In the prior art, there are two kinds of ways can reduce the rate of loss of isoprene greatly: 1. to reduce temperature of reaction, (this method is cost to increase energy consumption with improving production cost to prolong the reaction times.) 2. in sepn process, introduce stopper efficiently, inhibition of isoprenyl and other diolefin form multipolymer.

At present, in the inhibition five fractions of petroleum cracked carbon of using always there be the stopper of diolefin polymerization: o-NP, oil of mirbane, furfural, thanomin or Sodium Nitrite etc. that ZL96116289.9 introduces; Diethyl azanol and adjacent methyl hydroquinone that CN1699310A introduces.Generally select for use the principle of stopper to be: can effectively suppress diolefin autohemagglutination or copolymerization in reactor drum or knockout tower, be easy to again separate, thereby do not influence isoprene, m-pentadiene quality product; Again can be in gas phase Mulberry Extract, molecular weight that again can telomerized polymer makes logistics have good mobility; In the hot dimerization of petroleum cracking C 5 fraction, under the situation that does not influence the cyclopentadiene transformation efficiency, can effectively reduce the isoprene rate of loss.What time above consideration is, and above-mentioned stopper is not well suited for.

Summary of the invention

The purpose of this invention is to provide a kind of stopper that is used for suppressing the five fractions of petroleum cracked carbon diolefin polymerization; This stopper is specially adapted to the hot dimerization of diolefin in the five fractions of petroleum cracked carbon; It can effectively suppress the obstruction of diolefin autohemagglutination or copolymerization in hot dipolymer reactor, preheater; Can be in gas phase Mulberry Extract, molecular weight that again can telomerized polymer makes logistics have good mobility; In the hot dimerization of five fractions of petroleum cracked carbon, under the situation that does not influence the cyclopentadiene transformation efficiency, can effectively reduce the isoprene rate of loss.Simultaneously be easy to isolate the diolefin system again.

For solving the problem that reduces the isoprene rate of loss in the five fractions of petroleum cracked carbon in the hot dimerization of diolefin, adopt following technical scheme:

A kind of stopper that is used for suppressing the five fractions of petroleum cracked carbon diolefin polymerization, it is made up of DMKO, octanol and Ortho-Aminophenol.Be accurate measurement, preferably above-mentioned stopper be dissolved in five fractions of petroleum cracked carbon or the isoprene.The weight ratio of DMKO, octanol and Ortho-Aminophenol is 1: 0.01~10.0: 0.1~12.0, and DMKO, octanol and the Ortho-Aminophenol content in solvent is 1~20wt%.The weight ratio of DMKO, octanol and Ortho-Aminophenol is preferably 1: 2.0~and 8.0: 1.0~4.0, DMKO, octanol and the Ortho-Aminophenol total content in solvent is preferably 7~12wt%.

In the hot dimerization of five fractions of petroleum cracked carbon, in five fractions of petroleum cracked carbon, add above-mentioned stopper; When adding stopper, preferably adopt continuous pump to inject five fractions of petroleum cracked carbon, stopper is distributed in whole hot dipolymer reactor preferably.Inhibitor concentration is 50~1200ppm in the reactant, and optimum range is 200~600ppm.

Compared with prior art, stopper provided by the invention has better polymerization inhibition effect, and stopper can get in the gas phase, catches the radical that exists in the gas phase; In case formation polymkeric substance; Can avoid forming superpolymer; Make logistics keep good mobility; This stopper more can effectively suppress diolefin autohemagglutination or copolymerization in reactor drum or knockout tower in the petroleum cracking C 5 fraction, avoids preheater or reboiler to block, thus the stable operation cycle of extension fixture; In the hot dimerization of five fractions of petroleum cracked carbon, under the situation that does not influence the cyclopentadiene transformation efficiency, can effectively reduce the isoprene rate of loss.The stopper consumption is few, can reduce production costs; Various components of stopper and solvent and five fractions of petroleum cracked carbon boiling point differ bigger, thereby are easy to separate.

Embodiment

One, the preparation of stopper

Take by weighing DMKO, octanol and Ortho-Aminophenol in proportion, and be dissolved in solvent acetonitrile or the N.Control DMKO, octanol and Ortho-Aminophenol, the total content of three components is between 7~12wt%.Concrete DMKO, octanol and Ortho-Aminophenol weight ratio and the solvent of each embodiment specifies hereinafter.

Two, the evaluation test of stopper

Pressure at 3 250ml holds the petroleum cracking C 5 fraction that adds 200ml in the bullet respectively, with syringe the stopper for preparing is joined in the carbon five in the desired amount again, weighs; Install 3 blank that do not add stopper simultaneously, weigh.Put into water-bath, make an experiment, take out after the time and be cooled to room temperature by the temperature and time of design.3 pressure appearance bullets and 3 blank are moved in the vacuum drying oven, at 35 ℃ of following reduction vaporization 2h, vacuum tightness 0.08Mpa.Take out and weigh respectively, calculate the MV G1 that 6 pressure hold the polymer content in the bullet, calculate the MV G2 of the polymer content in 3 blank.

Stopper consumption (in the total amount of DMKO, octanol and Ortho-Aminophenol) and NSC 7352 yield, isoprene rate of loss specify in an embodiment.

Three, NSC 7352 yield and isoprene rate of loss method of calculation

The evaluation test of table 1 stopper is formed with petroleum cracking carbon Wuyuan material

Sequence number The component title Content (%wt) 1 Anti-butylene 2.04 2 Maleic 3.21 3 Pentamethylene 1.67 4 Iso-pentane 2.84 5 Skellysolve A 6.71

6 1 0.54 7 1,3-butadiene 5.56 8 3-methyl-1-butene 0.84 9 Cyclopentenes 4.50 10 Instead-the 2-amylene 2.94 11 The 2-methyl-2-butene 2.37 12 The 1-amylene 4.16 13 2-methyl-1-butene alkene 4.32 14 2-butyne 0.69 15 1, the 4-pentadiene 2.40 16 Isoprene 23.36 17 Cyclopentadiene 5.78 18 Along 1,3-pentadiene 6.70 19 Anti-1,3-pentadiene 11.95 20 X3 5.83 21 Benzene 0.34

[embodiment 1]

Component is DMKO, octanol and Ortho-Aminophenol, and solvent is a petroleum cracking carbon five.The weight ratio of DMKO, octanol and Ortho-Aminophenol is 1: 0.1: 0.2, inhibitor concentration 300ppm.Before adding stopper, the NSC 7352 yield: 96.62%, isoprene rate of loss: 22.39%; After adding stopper, the NSC 7352 yield: 95.93%, isoprene rate of loss: 15.12%.

[embodiment 2]

Component is DMKO, octanol and Ortho-Aminophenol, and solvent is a petroleum cracking carbon five.The weight ratio of DMKO, octanol and Ortho-Aminophenol is 1: 2.0: 3.0, inhibitor concentration 300ppm.Before adding stopper, the NSC 7352 yield: 96.62%, isoprene rate of loss: 22.39%; After adding stopper, the NSC 7352 yield: 95.89%, isoprene rate of loss: 16.40%.

[embodiment 3]

Component is DMKO, octanol and Ortho-Aminophenol, and solvent is a petroleum cracking carbon five.The weight ratio of DMKO, octanol and Ortho-Aminophenol is 1: 3.0: 2.0, inhibitor concentration 200ppm.Before adding stopper, the NSC 7352 yield: 96.62%, isoprene rate of loss: 22.39%; After adding stopper, the NSC 7352 yield: 96.86%, isoprene rate of loss: 18.63%.

[embodiment 4]

Component is DMKO, octanol and Ortho-Aminophenol, and solvent is a petroleum cracking carbon five.The weight ratio of DMKO, octanol and Ortho-Aminophenol is 1: 2.5: 2.5, inhibitor concentration 200ppm.Before adding stopper, the NSC 7352 yield: 96.62%, isoprene rate of loss: 22.39%; After adding stopper, the NSC 7352 yield: 96.75%, isoprene rate of loss: 19.26%.

[embodiment 5]

Component is DMKO, octanol and Ortho-Aminophenol, and solvent is a petroleum cracking carbon five.The weight ratio of DMKO, octanol and Ortho-Aminophenol is 1: 2.5: 2.5, inhibitor concentration 300ppm.Before adding stopper, the NSC 7352 yield: 96.62%, isoprene rate of loss: 22.39%; After adding stopper, the NSC 7352 yield: 96.19%, isoprene rate of loss: 16.42%.

[embodiment 6]

Component is DMKO, octanol and Ortho-Aminophenol, and solvent is a petroleum cracking carbon five.The weight ratio of DMKO, octanol and Ortho-Aminophenol is 1: 2.5: 2.5, inhibitor concentration 400ppm.Before adding stopper, the NSC 7352 yield: 96.62%, isoprene rate of loss: 22.39%; After adding stopper, the NSC 7352 yield: 95.87%, isoprene rate of loss: 14.23%.

[embodiment 7]

Component is DMKO, octanol and Ortho-Aminophenol, and solvent is a petroleum cracking carbon five.The weight ratio of DMKO, octanol and Ortho-Aminophenol is 1: 2.5: 2.5, inhibitor concentration 500ppm.Before adding stopper, the NSC 7352 yield: 96.62%, isoprene rate of loss: 22.39%; After adding stopper, the NSC 7352 yield: 95.02%, isoprene rate of loss: 12.16%.

[embodiment 8]

Component is DMKO, octanol and Ortho-Aminophenol, and solvent is a petroleum cracking carbon five.The weight ratio of DMKO, octanol and Ortho-Aminophenol is 1: 2.5: 2.5, inhibitor concentration 600ppm.Before adding stopper, the NSC 7352 yield: 96.62%, isoprene rate of loss: 22.39%; After adding stopper, the NSC 7352 yield: 94.85%, isoprene rate of loss: 10.17%.

[embodiment 9]

Component is DMKO, octanol and Ortho-Aminophenol, and solvent is an isoprene.The weight ratio of DMKO, octanol and Ortho-Aminophenol is 1: 3.0: 3.5, inhibitor concentration 400ppm.Before adding stopper, the NSC 7352 yield: 96.62%, isoprene rate of loss: 22.39%; After adding stopper, the NSC 7352 yield: 96.17%, isoprene rate of loss: 18.54%.

[embodiment 10]

Component is DMKO, octanol and Ortho-Aminophenol, and solvent is an isoprene.The weight ratio of DMKO, octanol and Ortho-Aminophenol is 1: 2.0: 4.0, inhibitor concentration 300ppm.Before adding stopper, the NSC 7352 yield: 96.62%, isoprene rate of loss: 22.39%; After adding stopper, the NSC 7352 yield: 96.29%, isoprene rate of loss: 17.26%.

[comparative example 1]

Component is a DMKO, inhibitor concentration 300ppm.Before adding stopper, the NSC 7352 yield: 96.62%, isoprene rate of loss: 22.39%; After adding stopper, the NSC 7352 yield: 96.58%, isoprene rate of loss: 16.52%.

[comparative example 2]

Component is an octanol, inhibitor concentration 300ppm.Before adding stopper, the NSC 7352 yield: 96.62%, isoprene rate of loss: 22.39%; After adding stopper, the NSC 7352 yield: 96.67%, isoprene rate of loss: 19.81%.

[comparative example 3]

Component is an Ortho-Aminophenol, inhibitor concentration 300ppm.Before adding stopper, the NSC 7352 yield: 96.62%, isoprene rate of loss: 22.39%; After adding stopper, the NSC 7352 yield: 95.95%, isoprene rate of loss: 15.67%.

Claims (5)

1. stopper that is used for the hot dimerization of five fractions of petroleum cracked carbon, it is characterized in that: it is made up of DMKO, octanol and Ortho-Aminophenol; The weight ratio of DMKO, octanol and Ortho-Aminophenol is 1: 0.01~10.0: 0.1~12.0; DMKO, octanol and the Ortho-Aminophenol content in solvent is 1~20wt%.
2. a kind of stopper that is used for the hot dimerization of petroleum cracking C 5 fraction according to claim 1; It is characterized in that: the weight ratio of DMKO, octanol and Ortho-Aminophenol is 1: 2.0~8.0: 1.0~4.0, and DMKO, octanol and the Ortho-Aminophenol total content in solvent is 7~12wt%.
3. a kind of stopper that is used for the hot dimerization of petroleum cracking C 5 fraction according to claim 1 is characterized in that: said solvent is petroleum cracking C 5 fraction or isoprene.
4. a kind of application that is used for the stopper of the hot dimerization of petroleum cracking C 5 fraction according to claim 1 is characterized in that: the consumption of stopper in five fractions of petroleum cracked carbon is 50~1200ppm by weight.
5. a kind of application that is used for the stopper of the hot dimerization of petroleum cracking C 5 fraction according to claim 4 is characterized in that: the consumption of stopper in five fractions of petroleum cracked carbon is 200~600ppm by weight.
CN201010535960XA 2010-11-04 2010-11-04 Polymerization inhibitor used in thermal dimerization process of petroleum cracking C5 fraction CN102464555B (en)

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CN106179122A (en) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 The consersion unit of alkadienes and application thereof

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Publication number Priority date Publication date Assignee Title
US5907071A (en) * 1998-04-21 1999-05-25 Betzdearborn Inc. Compositions and methods for inhibiting vinyl aromatic monomer polymerization
CN1324338A (en) * 1998-11-05 2001-11-28 贝茨迪尔博恩公司 Methods and compositions for inhibiting polymerization of ethylenically unsaturated hydrocarbons
CN1490286A (en) * 2002-10-16 2004-04-21 中国石油化工股份有限公司 Separating method for cracking C5-fraction

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106179122A (en) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 The consersion unit of alkadienes and application thereof
CN106179122B (en) * 2015-04-30 2019-06-28 中国石油化工股份有限公司 The consersion unit of alkadienes and its application

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