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CN1102848A - Antiscalants for petrochemical processing - Google Patents

Antiscalants for petrochemical processing Download PDF

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Publication number
CN1102848A
CN1102848A CN94107845A CN94107845A CN1102848A CN 1102848 A CN1102848 A CN 1102848A CN 94107845 A CN94107845 A CN 94107845A CN 94107845 A CN94107845 A CN 94107845A CN 1102848 A CN1102848 A CN 1102848A
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Prior art keywords
petrochemical
scale
plant
preventing
scale inhibitor
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CN94107845A
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CN1110534C (en
Inventor
田中浩一
入江胜利
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Kurita Water Industries Ltd
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Kurita Water Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/14—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means
    • C10G9/16—Preventing or removing incrustation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G7/00—Distillation of hydrocarbon oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
    • C10G75/04—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general by addition of antifouling agents

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

本发明涉及由授氢氢化芳族化合物组成的用于 石油化学加工的防垢剂。本发明防垢剂易于处理，便 宜，对加工过程无反作用，具有出色的防止污垢形成 的作用，并且能在良好稳定性下连续使设备操作一段 长时间。The present invention relates to a composition consisting of a hydrogen-donating hydrogenated aromatic compound for use in Antiscalants for petrochemical processing. The antifouling agent of the present invention is easy to handle, just suitable, has no adverse effect on the processing process, and has excellent prevention of fouling formation function, and can continuously operate the equipment for a period of time under good stability long time.

Description

An antifoulant for petrochemical processes
The present invention relates to a kind of novel scale inhibitor that is used for petroleum chemistry processing.Be particularly related to a kind of scale inhibitor that is used for petroleum chemistry processing, this scale inhibitor can prevent in the technological process of petrochemical factory effectively such as generate dirt in the treating process of ethylene production factory.
Petrochemical plant such as ethylene production factory in, the fluid that contains alkene such as ethene and propylene and diolefins such as divinyl is distilled, in such fluidic still-process, this fluid must be with heat modification in addition, form sludge by heat, for example in preheat exchanger or reboiler, and the sludge that forms so just sticks on the heat-transfer surface of preheat exchanger or reboiler; Perhaps adhere on the surface of pipeline and form dirt.
The mechanism that forms as dirt has following known phenomenon:
In petrochemical process, organic compound in working fluid is easy to oxidation such as the compound as alkene and diolefins in the unsaturated hydrocarbons, these compounds cause the generation of hydroperoxide in working fluid owing to dissolved oxygen, these hydroperoxide are decomposes then, particularly form ketone, aldehyde, carboxylic acid etc. in the presence of material such as the metal that the band catalytic activity is arranged, these compounds are aggregated and form oligopolymer and polymkeric substance sludge.
Therefore, use antioxidant such as phenol antioxidant and amine antioxidants, polymerization retarder such as oximes inhibitor and nitroso-group inhibitor, prevent to form sludge and throw out agglutinating dispersion agent and the medicament that is used in combination with these medicaments in petrochemical process as scale inhibitor, its purpose just is to prevent aforesaid dirt.For example: (1) by aniline and tert-butyl catechol in conjunction with and the scale inhibitor formed [Japan speciallys permit communique, clear and 59(1984)-24138; ] (2) scale inhibitor of forming by nitrosophenol [Japan's special permission is open, put down into 3(1991)-350147]; (3) scale inhibitor be made up of aminated compounds of the scale inhibitor of being made up of nitroso compound [Japanese specail comment communique is put down into 4(1992)-26639] and (4) [Japan's special permission is open, clear and 64(1989)-13041] all disclosed already.
Yet because these scale inhibitors directly are added in the operating process, their shortcoming is: make product painted; Form unfavorable by product; And then they are difficult for handling; These scale inhibitors; Its antiscaling effect is insufficient, thereby, one segment length's time of operate continuously such as 2 years or the longer time in go wrong.
As mentioned above, scale inhibitor commonly used is often unsatisfactory, and therefore, people wish to develop a kind of scale inhibitor that is used for petroleum chemistry processing strongly, and this scale inhibitor is easy to handle; Cheaply; Technological process there is not retroaction; Preventing that dirt from forming and have the chromatic effect of going out and can one segment length's time of operate continuously under good stability.
The object of the invention is: a kind of scale inhibitor that is used for petroleum chemistry processing is provided, this scale inhibitor overcomes the shortcoming of the habitual scale inhibitor that is used for petroleum chemistry processing, be easy to handle, cheaply, for course of processing low-disturbance, preventing that dirt from demonstrating chromatic effect on forming, can make equipment one segment length's time of operate continuously under good stability.
The inventor has in development on the scale inhibitor that is used for petroleum chemistry processing of above-mentioned premium properties and has done extensive and deep research.Like that, find that the object of the invention can award the hydrogen hydroaromatic compound and reach by containing shown in this result of study, the present invention is accomplished on this finds.
Therefore, the invention provides a kind of scale inhibitor of awarding hydrogen hydrogen aromatic substance that contains that is used for petroleum chemistry processing.
The present invention also provides a kind of method that prevents to generate dirt in petroleum chemistry equipment, and this method comprises: the above-mentioned scale inhibitor that is used for petroleum chemistry processing is added to the working fluid that is supplied to the petrochemical process of giving birth to dirt.
Other purposes of the present invention, characteristic and advantage will be clear more fully in the following description.
As mentioned above, the formation of dirt be in working fluid by radical chain reaction by due to the oxidation of the unsaturated hydrocarbons of alkene and diolefins.The hydrogen hydroaromatic compound of awarding as scale inhibitor has following function in the present invention: make chain reaction end and prevent from effectively to give birth to dirt by the group that produces is granted proton in oxidation.Comprise as the example of awarding the hydrogen hydroaromatic compound: 1,2,3,4 ,-tetraline, 9,10-dihydro phenanthrene, 1,2,3,4,5,6,7,8-eight phenanthrene and hydrogenated terphenyl, these compounds can use separately or two or more compound combines use.
In scale inhibitor of the present invention, except that the hydrogenation aromatic hydrocarbon, also can use conventional scale inhibitor as required, such as: the antioxidant as amine antioxidants and phenols oxidation inhibitor, poly-inhibitor, metal deactivator and the various dispersion agent of containing as oximes inhibitor and nitroso-group inhibitor.Dispersion agent is scattered in organic sludge and inorganic sludge in the process fluid, and prevents that throw out is bonded on heat transmitter or the pipeline surface.Dispersion agent comprises:
(1) having molecular weight is about 1000 to 10000 poly-alkyl (methyl) acrylate and by the mixture of the represented polyethylene polyamine cycloalkanoimide of following general formula:
Figure 941078450_IMG1
Wherein, R 1Hydrocarbyl group, n that representative has 10 to 15 carbon atoms represent 1 to 5 integer, and preferably 1 to 3, m represents 1 to 10 integer, and is best 1 to 3, and the weight ratio of each compound is in 90: 10 to 10: 90 scopes in the mixture;
(2) by the represented succinimide derivatives of one of following general formula:
Wherein, R 2It is 400 to 3000 polybutene group that expression has nucleidic mass, R 3Expression has 1 to 5 carbon atom, is preferably the imine group of 1 to 3 carbon atom, R 4And R 5Expression is respectively for hydrogen atom or have that carbon atom is 1 to 5, the groups of best 1 to 3 carbon atom, and P represents 1 to 10 integer.
(3) by the phosphorothioate derivative of following general formula representative or its ethylene oxide adduct:
Figure 941078450_IMG3
Wherein, R 6Be that to have nucleidic mass be 500 to 2000 polybutene group; And
(4) having nucleidic mass is 10,000 to 1,000,000 vinylbenzene and maleate copolymer, and it represents general formula as follows:
Figure 941078450_IMG4
Wherein, R 7And R 8Each representative has the straight or branched alkyl or the alkenyl of 12 to 18 carbon atoms, and q and r represents digital, two kinds of unitary mol ratios of this numeral (q: r) in 1: 9 to 9: 1 scope, can use two kinds or two or more dispersion agents as required.
The example that is used for poly-alkyl (methyl) acrylate of above-mentioned dispersion agent (1) comprises having the alkyl that carbonatoms is 5 to 18 alkyl (methyl) Voncoat R 3310, the multipolymer that co-polymerization by two or more said alkyl (methyl) acrylate obtains, and the multipolymer that obtains with the co-polymerization of unsaturated monomer such as N-vinyl-2 pyrrolidone of one or more insatiable hunger key and diethylaminoethyl-(methyl) acrylate by one or more said alkyl (methyl) acrylate with alkene.
The amount of the various components in scale inhibitor is used as required, and such as antioxidant, polymeric inhibitor, metal deactivator and dispersion agent are not limited especially, as long as suitably selected.The working fluid that adds scale inhibitor of the present invention is not limited especially yet, and scale inhibitor of the present invention can be added in the pending oil of any kind of, in this oil, forms dirt when handling in petroleum chemistry processing.Scale inhibitor of the present invention preferably puts in the work oil of handling in preheat exchanger or the reboiler in distillation tower, in the depropanizer on ethylene unit, deethanizer, debutanizer or condensation stripping tower.
Below the best approach example that applies scale inhibitor of the present invention is described.The annexing ingredient of awarding hydrogen hydroaromatic compound and other component such as other scale inhibitor and use in addition as required is dissolved in the appropriate solvent, has concentration about 0.5 to 60(weight so that be mixed with) solution of %.The solution of so preparation is made an addition in the device of formation dirt in petroleum chemistry processing, such as heat exchanger, reboiler or pipeline continuously; Perhaps be added in the raw material oil groove to a full dose.The addition of scale inhibitor of the present invention in working fluid generally selected according to the scope of 0.5 to 50000 milligram every liter of amount of working fluid, best 30 to 200 milligrams.
Because scale inhibitor of the present invention has the outstanding performance of antiscale, therefore make equipment one segment length's time of operate continuously under good stability become possibility such as 2 years to 3 years, compare only three months power lifetime of the latter with conventional scale inhibitor.The result can expect energy-conservation and lower maintenance cost, and then can prevent to be accompanied by the caused shut-down of accident.
It is as follows to sum up advantage of the present invention: the scale inhibitor that is used for petroleum chemistry processing is easy to handle, cheaply, to course of processing low-disturbance, preventing to form the outstanding effect of demonstration on the dirt, make equipment operate continuously one segment length under good stability the time become possibility, and energy-conservation and reduction maintenance cost.
Will be with reference to the following example to the present invention's easy to understand more, however these embodiment are used to set forth the present invention and can not be considered to limit the scope of the invention.
Embodiment 1 to 6 and comparative example 1 are as follows to 4:
The medicament that is shown in various types of and each quantity of table 1 is added in the depropanizer bottom flow of taking from a just on-stream device, this mixture is poured in 200 milliliters of autoclaves of the stainless steel of SUS304, handled 20 hours down at 100 ℃, under reduced pressure distill this processed fluid then, obtain residue on evaporation amount (amount of polymers of formation) after the drying.The inhibiting rate that dirt forms is according to above-mentioned income value the ratio that derives from the analog value that does not contain above-mentioned medicament to be calculated, and is used for evaluating its anti-scaling property.
In table 1, used dispersion agent is that to have nucleidic mass be 15000 vinylbenzene and the multipolymer of maleic acid ester and the tert-butyl catechol of representing with TBC.
Comparative example 1 and 2 shows good result on the inhibiting rate that dirt forms, yet in fact contraposition one nitro-0-cresols can not use, because it has problem on handling.
Figure 941078450_IMG5

Claims (11)

1、用于石油化学加工的防垢剂含有授氢氢化芳族化合物。1. Antiscalants used in petrochemical processing contain hydrogenated hydrogenated aromatic compounds. 2、按照权利要求1所说的用于石油化学加工的防垢剂，其中，授氢氢化芳族化合物是选自下列一组化合物的一种化合物：1，2，3，4，-四氢化萘、9，10-二氢菲、1，2，3，4，5，6，7，8-八氢菲和氢化三联苯。2. The antiscalant agent for petrochemical processing according to claim 1, wherein the hydrogenated hydrogenated aromatic compound is a compound selected from the following group of compounds: 1,2,3,4,-tetrahydrogenated Naphthalene, 9,10-dihydrophenanthrene, 1,2,3,4,5,6,7,8-octahydrophenanthrene and hydrogenated terphenyls. 3、按照权利要求1所说的用于石油化学加工的防垢剂，其中，所说的防垢剂含有分散淤渣用的分散剂。3. The antiscalant agent for petrochemical processing according to claim 1, wherein said antiscalant agent contains a dispersant for dispersing sludge. 4、按照权利要求3所说的用于石油化学加工的防垢剂，其中，所说的分散淤渣用的分散剂至少选自下列一组化合物中的一种：聚烷基（甲基）丙烯酸酯和多亚乙基多胺环烷酸酰胺的混合物、琥珀酸酰胺衍生物、硫代磷酸酯衍生物或它的环氧乙烷加成物以及苯乙烯和马来酸酯的共聚物。4. The antiscalant agent for petrochemical processing according to claim 3, wherein said dispersant for dispersing sludge is at least one selected from the following group of compounds: polyalkyl(methyl) Mixtures of acrylates and polyethylene polyamine naphthenic amides, succinic acid amide derivatives, phosphorothioate derivatives or their ethylene oxide adducts and copolymers of styrene and maleic acid esters. 5、防止在石油化学装置中生垢的方法，其中包括将权利要求1所说的防垢剂加到供应给生垢的石油化学加工过程的工作流体之中。5. A method for preventing scale formation in a petrochemical plant, which comprises adding the scale inhibitor as claimed in claim 1 to a working fluid supplied to a scale-forming petrochemical process. 6、按照权利要求5所说的防止在石油化学装置中生垢的方法，其中，将用于石油化学加工的防垢剂以0.5到50，000毫克/升范围的量加到工作流体之中。6. The method for preventing scale formation in a petrochemical plant according to claim 5, wherein the scale inhibitor for petrochemical processing is added to the working fluid in an amount ranging from 0.5 to 50,000 mg/liter . 7、按照权利要求5所说的防止在石油化学装置中生垢的方法，其中，将用于石油化学加工的防垢剂在形成污垢的装置进入石油化学设备之前连续地添加于工作流体之中。7. The method for preventing scale formation in a petrochemical plant according to claim 5, wherein the scale inhibitor for petrochemical processing is continuously added to the working fluid before the scale-forming plant enters the petrochemical plant . 8、按照权利要求5所说的防止在石油化学设备中生垢的方法，其中，将用于石油化学加工的防垢剂添加于石油化学设备的工作流体的原料槽中。8. The method for preventing scale formation in petrochemical equipment according to claim 5, wherein an anti-scale agent for petrochemical processing is added to a raw material tank of a working fluid of the petrochemical equipment. 9、按照权利要求5所说的防止在石油化学设备中生垢的方法，其中，所说的石油化学设备是乙烯设备。9. The method for preventing scale formation in a petrochemical plant according to claim 5, wherein said petrochemical plant is an ethylene plant. 10、按照权利要求5所说的防止在石油化学设备中生垢的方法，其中，所说的防垢剂含有用于分散淤渣的分散剂。10. The method for preventing scale formation in petrochemical equipment according to claim 5, wherein said scale preventive agent contains a dispersant for dispersing sludge. 11、按照权利要求10所说的防止在石油化学设备中生垢的方法，其中，所说的用于分散淤渣的分散剂至少选自下列一组药剂中的一种：聚烷基（甲基）丙烯酸酯和多亚乙基多胺环酸酰胺的混合物、琥珀酸酰胺衍生物、硫代磷酸酯衍生物或它的环氧乙烷加成物以及苯乙烯和马来酸酯的共聚物。11. The method for preventing scaling in petrochemical equipment according to claim 10, wherein said dispersant for dispersing sludge is at least one selected from the following group of agents: polyalkylene (form base) a mixture of acrylate and polyethylene polyamine cyclic acid amides, succinic acid amide derivatives, phosphorothioate derivatives or its ethylene oxide adducts, and copolymers of styrene and maleate .
CN94107845A 1993-07-01 1994-07-01 An antifoulant for petrochemical processes Expired - Fee Related CN1110534C (en)

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JP189249/1993 1993-07-01
JP5189249A JPH0718265A (en) 1993-07-01 1993-07-01 Antifouling agent for petrochemical process

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Cited By (2)

* Cited by examiner, † Cited by third party
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CN110452786A (en) * 2019-08-07 2019-11-15 南京汇达化工有限公司 Add hydrogen antiscale agent prescription and its production method
CN114729270A (en) * 2019-11-27 2022-07-08 埃科莱布美国股份有限公司 Antifouling compositions for crude oil production and processing

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JP2007106926A (en) * 2005-10-14 2007-04-26 Hakuto Co Ltd Antifouling agent for oil refining and antifouling method for oil refining plant
US9200213B2 (en) * 2008-03-24 2015-12-01 Baker Hughes Incorporated Method for reducing acids in crude or refined hydrocarbons
US9108832B2 (en) 2009-11-04 2015-08-18 Hitachi High Technologies Corporation Cover opener and automatic analyzing device using same
EP2581421A1 (en) 2011-10-12 2013-04-17 Ineos Europe AG Additive
KR102404839B1 (en) 2016-08-25 2022-06-07 비엘 테크놀러지스 인크. Reduce contamination of hydrocarbon oils
CN110337488B (en) * 2017-02-27 2021-11-16 埃科莱布美国股份有限公司 Antifouling agent formulation for compressor
KR102374179B1 (en) * 2017-05-09 2022-03-14 카타야마 케미칼, 인코포레이티드 Methods for preventing contamination of heat exchangers in petroleum processes
US20230407196A1 (en) * 2020-09-30 2023-12-21 Sabic Global Technologies B.V. Application of surfmers to mitigate fouling in olefins plants

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Publication number Priority date Publication date Assignee Title
CN110452786A (en) * 2019-08-07 2019-11-15 南京汇达化工有限公司 Add hydrogen antiscale agent prescription and its production method
CN114729270A (en) * 2019-11-27 2022-07-08 埃科莱布美国股份有限公司 Antifouling compositions for crude oil production and processing

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EP0632121A3 (en) 1995-05-17
EP0632121B1 (en) 2000-03-01
KR0140052B1 (en) 1998-06-15
EP0632121A2 (en) 1995-01-04
JPH0718265A (en) 1995-01-20
CN1110534C (en) 2003-06-04
KR950003422A (en) 1995-02-16
DE69423140T2 (en) 2000-08-24
BR9402609A (en) 1995-04-04

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