JPS63221185A - Contamination inhibitor used in petroleum refining - Google Patents
Contamination inhibitor used in petroleum refiningInfo
- Publication number
- JPS63221185A JPS63221185A JP5497387A JP5497387A JPS63221185A JP S63221185 A JPS63221185 A JP S63221185A JP 5497387 A JP5497387 A JP 5497387A JP 5497387 A JP5497387 A JP 5497387A JP S63221185 A JPS63221185 A JP S63221185A
- Authority
- JP
- Japan
- Prior art keywords
- antifouling agent
- phosphite ester
- branched alkyl
- styrene
- alkenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000005504 petroleum refining Methods 0.000 title claims abstract description 8
- 238000011109 contamination Methods 0.000 title abstract description 6
- 239000003112 inhibitor Substances 0.000 title abstract 4
- 229920001577 copolymer Polymers 0.000 claims abstract description 15
- 150000008301 phosphite esters Chemical group 0.000 claims abstract description 13
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000002519 antifouling agent Substances 0.000 claims description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 6
- 150000001412 amines Chemical class 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 2
- 229930195733 hydrocarbon Natural products 0.000 abstract description 2
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 239000004615 ingredient Substances 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 8
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910001120 nichrome Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000010802 sludge Substances 0.000 description 5
- 230000003373 anti-fouling effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229960002317 succinimide Drugs 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 229920001281 polyalkylene Polymers 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QVGXLLKOCUKJST-BJUDXGSMSA-N oxygen-15 atom Chemical compound [15O] QVGXLLKOCUKJST-BJUDXGSMSA-N 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は石油精製プロセスにおいて生成する汚れを防
止するための汚れ防止剤に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] This invention relates to an antifouling agent for preventing fouling generated in petroleum refining processes.
石油精製プロセスにおいては、常圧蒸留装置、水素化脱
硫装置、接触改質装置等積々のプロセスがあり、石油か
ら各石油製品がつくられるまで各原料油は加熱、冷却１
分解、分離等が繰り返し行われる。これら装置において
は、予熱熱交換器、加熱炉等で加熱する時に、原料油が
熱変性を受けてスラッジが生成し、これが器壁に付着し
°〔汚れが生成する。特に各原料油を船舶輸送するよう
な場合、あるいは中間タンクに原料油を一度スドックす
るような場合には、原料油中に酸素が溶解するが、酸素
を含んだ原料油を処理すると、著しく汚れが増大する。In the oil refining process, there are many processes such as atmospheric distillation equipment, hydrodesulfurization equipment, catalytic reforming equipment, etc., and each raw material oil is heated, cooled,
Decomposition, separation, etc. are performed repeatedly. In these devices, when heated in a preheating heat exchanger, heating furnace, etc., the raw material oil undergoes thermal denaturation to generate sludge, which adheres to the vessel walls and forms dirt. Oxygen is dissolved in the feedstock, especially when each feedstock is transported by ship or once stocked in an intermediate tank, but when feedstock containing oxygen is processed, it becomes extremely polluted. increases.
石油精製プロセスでは上記各装置の熱交換器、加熱炉、
配管等に起きる原料油に起因する汚れの防止を目的とし
て酸化防止剤、金属不活性剤、分散剤など、あるいはそ
れらを組合わせた汚れ防止剤が用いられている。従来の
汚れ防止剤の代表的なものとしてポリアルケニルコハク
酸イミドが知られているが、このほかアルキルまたはア
ルケニル置換有機カルボン酸およびポリアルキレンポリ
アミンの共重合体とホスファイトとを含む汚れ防止剤が
知られている（例えば特公昭４６−６５０３号）。In the oil refining process, the heat exchangers, heating furnaces,
Anti-fouling agents such as antioxidants, metal deactivators, dispersants, or combinations thereof are used to prevent stains caused by raw material oil that occur in piping and the like. Polyalkenylsuccinimide is known as a typical conventional antifouling agent, but there are also antifouling agents containing copolymers of alkyl- or alkenyl-substituted organic carboxylic acids and polyalkylene polyamines, and phosphites. It is known (for example, Japanese Patent Publication No. 46-6503).
しかしながら従来のポリアルケニルコハク酸イミド等の
汚れ防止剤では、汚れの度合いが低い場合には、何とか
汚れを抑制できるが、汚れの度合いが高まるにつれて汚
れ防止効果が得られなくなる。また特公昭４６−６５０
３号の組成物はポリアルキレンポリアミンを含むもので
あるため１石油精製時の温度下でアミンが分解する。こ
うして生成したアミンは石油精製のときに用いられる触
媒に対して触媒毒となるため通常は使用できず、使用さ
れるとしても極めて少量に制限されるなどの問題点があ
った。However, conventional antifouling agents such as polyalkenyl succinimide can somehow suppress staining when the degree of contamination is low, but as the degree of contamination increases, the antifouling effect becomes less effective. Also, special public service 1976-650
Since composition No. 3 contains polyalkylene polyamine, the amine decomposes at the temperature used in petroleum refining. The amines produced in this way poison the catalysts used in petroleum refining, so they cannot normally be used, and even if they are used, they are limited to very small amounts.
この発明は上記のような問題点を解決するためのもので
、汚れ防止効果が高く、かつ分解によりアミンが生成し
ない石油精製用汚れ防止剤を提供することを目的として
いる。This invention is intended to solve the above-mentioned problems, and aims to provide an antifouling agent for petroleum refining that has a high antifouling effect and does not produce amines upon decomposition.
本発明は、スチレン−マレイン酸エステル共重合体と、
第２級または第３級ホスファイトエステルとを含むこと
を特徴とする石油精製用汚れ防止剤である。The present invention provides a styrene-maleic acid ester copolymer,
This is an antifouling agent for petroleum refining, characterized in that it contains a secondary or tertiary phosphite ester.
本発明における一方の成分であるスチレン−マレイン酸
エステル共重合体はスチレンとマレイン酸の共重合体で
あり、特に次式
（ただしＲいＲ２はそれぞれ炭素数１２〜１８の直鎖も
しくは分岐アルキル基またはアルケニル基、■：ｎ（モ
ル比）＝１：９〜９：１である。）で表わされる分子、
ｉ＋ｎｏ、ｏｏｏ−ｉ、ｏｏｏ、ｏｏｏの共重合体が好
ましい。The styrene-maleic acid ester copolymer, which is one of the components in the present invention, is a copolymer of styrene and maleic acid, and is particularly represented by the following formula (where R and R2 are each a linear or branched alkyl group having 12 to 18 carbon atoms). or an alkenyl group, (■:n (molar ratio) = 1:9 to 9:1),
Copolymers of i+no, ooo-i, ooo, and ooo are preferred.
式（１）において、Ｒ１，Ｒ，で表わされるアルキル基
またはアルケニル基としては、ドデシル基、トリデシル
基、テトラデシル基、ペンタデシル基、ヘキサデシル基
、ヘプタデシル基、オクタデシル基、オレイル基などが
あり、それぞれ同一のものでも別のものでもよい。ｍ：
ｎ（モル比）はｌ：９〜９：１、好ましくは２：８〜８
：２である。In formula (1), the alkyl group or alkenyl group represented by R1, R, includes dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, oleyl group, etc. It can be something else or something else. m:
n (molar ratio) is l:9 to 9:1, preferably 2:8 to 8
:2.
本発明における他の成分である第２級または第３級ホス
ファイトエステルは亜りん酸の２〜３個の酸基がエステ
ル化したものであり、特に次式（ただしＲ１は水素また
は炭素数８〜１８の直鎖もしくは分岐アルキル基または
アルケニル基、Ｒ２，Ｒ３は炭素数８〜１８の直鎖もし
くは分岐アルキル基またはアルケニル基である。）
で表わされる分子量３００〜６００のものが好ましい。The secondary or tertiary phosphite ester, which is another component in the present invention, is an esterified product of 2 to 3 acid groups of phosphorous acid, and is particularly represented by the following formula (where R1 is hydrogen or has 8 carbon atoms). to 18 straight chain or branched alkyl groups or alkenyl groups, R2 and R3 are straight chain or branched alkyl groups or alkenyl groups having 8 to 18 carbon atoms, and those having a molecular weight of 300 to 600 are preferred.
式（ＩＩ）において、ＲいＲ２、Ｒ１で表わされるアル
キル基またはアルケニル基としては、式ＣＩ］において
例示したもののほかに、オクチル基、ノニル基、デシル
基、ウンデシル基、ウンデシル基などがあり、それぞれ
同一のものでも別のものでもよい。In formula (II), the alkyl group or alkenyl group represented by R2 and R1 includes, in addition to those exemplified in formula CI], an octyl group, a nonyl group, a decyl group, an undecyl group, an undecyl group, etc. They may be the same or different.
前記共重合体と第２級または第３級ホスファイトエステ
ルの配合比は重址比で１：９〜９：ｌ、好ましくは２５
： ７５〜７５ ： ２５、さらに好ましくは５０
： ５０〜７５ ： ２５が適当である。本発明の汚れ
防止剤は上記成分以外に他の成分を含んでいてもよい。The mixing ratio of the copolymer and the secondary or tertiary phosphite ester is 1:9 to 9:l, preferably 25
: 75-75 : 25, more preferably 50
: 50-75 : 25 is appropriate. The antifouling agent of the present invention may contain other components in addition to the above components.
本発明の汚れ防止剤の処理対象となるのは、石油精製プ
ロセス系のうち汚れの発生するすべての系があげられる
が、特に原油常圧蒸留装置、ナフサ、灯軽油水素化脱硫
装置、ＦＣＣなどの原料油熱交換器の系が処理に適して
いる。本発明の汚れ防止剤の使用方法は、上記配合の汚
れ防止剤を炭化水素系溶媒に溶解し１石油精製プロセス
系で汚れが発生している熱交換器の前に連続注入する。The antifouling agent of the present invention can be used to treat all oil refining process systems where fouling occurs, but in particular, crude oil atmospheric distillation equipment, naphtha, kerosene and gas oil hydrodesulfurization equipment, FCC, etc. A system of feedstock heat exchangers is suitable for the treatment. The method for using the antifouling agent of the present invention is to dissolve the antifouling agent of the above composition in a hydrocarbon solvent and continuously inject the solution in front of a heat exchanger where fouling occurs in an oil refining process system.
汚れ防止剤の使用濃度は３〜５００＋＋＋ｇ／ｋｇ（対
処理オイル）Ｐｉ度である。The concentration of the antifouling agent used is 3 to 500 +++ g/kg (to treated oil) Pi degrees.
本発明の汚れ防止剤を添加すると、スチレン−マレイン
酸エステル共重合体はその極性により生成スラッジを変
性させて付着性を減少させ、また第２級または第３級ホ
スファイトエステルは、酸化防止作用によりヒドロペル
オキシドを分解してスラッジの生成を抑制し、これらが
相乗的に作用し合って、スラッジの生成を抑制すると同
時にスラッジの付着を防止し、これにより優れた汚れ防
止効果が得られる。一般に酸素が溶存したナフサ、灯軽
油を処理する水素化脱硫装置においては、汚れ防止剤無
添加の場合、汚れ付着により数カ月しか運転できず、ま
たポリアルケニルコハク酸イミド等の既存の汚れ防止剤
を使用する場合でも、せいぜい半年ぐらいしか運転でき
ないが、本発明の汚れ防止剤の場合、約１年の運転が可
能となる。When the antifouling agent of the present invention is added, the styrene-maleate ester copolymer modifies the formed sludge due to its polarity and reduces adhesion, and the secondary or tertiary phosphite ester has an antioxidant effect. This decomposes hydroperoxides and suppresses the formation of sludge, and these act synergistically to suppress the formation of sludge and at the same time prevent the adhesion of sludge, thereby providing an excellent antifouling effect. In general, hydrodesulfurization equipment that processes naphtha and kerosene with dissolved oxygen can only be operated for a few months without the addition of antifouling agents due to fouling, and existing antifouling agents such as polyalkenyl succinimide can be used without the addition of antifouling agents. Even if it is used, it can only be operated for about half a year at most, but in the case of the antifouling agent of the present invention, it can be operated for about one year.
このため熱交換器での汚れが軽減でき、装置の安定運転
と省エネルギーが可能となる。Therefore, contamination in the heat exchanger can be reduced, making it possible to operate the device stably and save energy.
以上の通り、本発明によれば、スチレン−マレイン酸エ
ステル共重合体と第２Ｒまたは第３Ｒホスフアイトエス
テルを有効成分としたため、両成分の相乗作用により優
れた汚れ防止効果が得られ、これにより酸素を溶存する
場合および汚れの度合が高い場合でも効率よく汚れを防
止できるという効果がある。As described above, according to the present invention, since the styrene-maleate ester copolymer and the 2R or 3R phosphite ester are used as active ingredients, an excellent stain prevention effect is obtained due to the synergistic action of both components. It has the effect of efficiently preventing stains even when oxygen is dissolved or when the degree of stain is high.
以下、本発明の実施例について説明する。 Examples of the present invention will be described below.
実施例１
スチレン−マレイン酸エステル共重合体として、）ｉ１
＝Ｒ，＝＝Ｃ１，ｌｔ、、 ＠： ｎ＝１ ： １．分
子ｉ ５０ 、０００のものを用い、ホスファイトエス
テルとして、Ｒ１＝Ｈ。Example 1 As a styrene-maleic acid ester copolymer, )i1
=R,==C1,lt,, @: n=1: 1. A molecule of i 50 ,000 is used, and as a phosphite ester, R1=H.
Ｒ−”Ｒ３＝Ｃｘ−Ｈ３ｓのものを用い、これらを表１
に示す配合比（重量比）で試料油としての軽油に添加し
てホットワイヤ試験を行った。R-"R3=Cx-H3s, and these are shown in Table 1.
A hot wire test was conducted by adding it to light oil as a sample oil at the blending ratio (weight ratio) shown in .
第１＠はホットワイヤ試験法を示す構成図で、試料１の
入った３個のビー力２をオイルバス３に浸漬し、試料１
中に支持棒４によりニクロム線５をセットし、電圧調整
器６を介して電源から一定電流をニクロム１！５に流し
、ニクロム線５に付着した汚れを測定する。このときの
試料容ｔｈ１４００ｍｊｌ、温度１５０℃、電圧２．６
Ｖ＋電流７．５Ａ、試験時間３日、薬剤濃度２０ｔｍｇ
／ ｎであり、結果を表１に示す。The first @ is a configuration diagram showing the hot wire test method, in which three beers 2 containing sample 1 are immersed in an oil bath 3.
A nichrome wire 5 is set inside the nichrome wire 5 using a support rod 4, and a constant current is passed through the nichrome 1!5 from a power source via a voltage regulator 6 to measure the dirt attached to the nichrome wire 5. At this time, sample volume th1400mjl, temperature 150℃, voltage 2.6
V+ current 7.5A, test time 3 days, drug concentration 20tmg
/n, and the results are shown in Table 1.
表１
実施例２
実施例１の汚れ防止剤（共重合体：ホスファイトエステ
ル配合比１：１）を試料油としての軽油に添加して加熱
ブロック試験を行った。Table 1 Example 2 The antifouling agent of Example 1 (copolymer:phosphite ester blending ratio 1:1) was added to light oil as a sample oil, and a heating block test was conducted.
第２図は加熱ブロック試験法を示す構成図で、出口温度
が制御できる第１および第２ヒータブロツク７．８に試
験チューブ９およびヒータｌＯをセットし、試料タンク
１１から試料１をポンプ１２により一定流量で流し、冷
却器１３を通して循環し、試験チューブ９に付着する汚
れを測定する。１４は圧力計、 １５は保圧弁である。FIG. 2 is a configuration diagram showing the heating block test method, in which the test tube 9 and heater lO are set in the first and second heater blocks 7.8 whose outlet temperature can be controlled, and the sample 1 is pumped from the sample tank 11 by the pump 12. It flows at a constant flow rate, circulates through the cooler 13, and measures the dirt adhering to the test tube 9. 14 is a pressure gauge, and 15 is a pressure holding valve.
このときの試料流量１Ω／ｈｒ、温度１５０−）２５０
℃、溶存酸素１５ｍｇ／ｋｇ、試験時間３日であり、結
果を表２に示す。同様に汚れ防止剤として従来品のポリ
ブテニルコハク酸イミドを添加した場合、ならびに汚れ
防止剤無添加の場合の結果を併記する。At this time, the sample flow rate was 1Ω/hr, the temperature was 150-250
℃, dissolved oxygen 15 mg/kg, test time 3 days, and the results are shown in Table 2. Similarly, the results when conventional polybutenyl succinimide was added as an antifouling agent and when no antifouling agent was added are also shown.
表２
以上の結果より、本発明の汚れ防止剤は相乗効果を有し
、溶存酸素が存在する系でも優れた汚れ防止効果が得ら
れることがわかる。Table 2 From the above results, it can be seen that the antifouling agent of the present invention has a synergistic effect, and an excellent antifouling effect can be obtained even in systems where dissolved oxygen is present.
第１図および第２図は実施例における試験方法を示す構
成図であり、１は試料、３はオイルバス、５はニクロム
線、７．８はヒータブロック、９は試験チューブ、１０
はヒータである。1 and 2 are configuration diagrams showing the test method in the example, in which 1 is a sample, 3 is an oil bath, 5 is a nichrome wire, 7.8 is a heater block, 9 is a test tube, 10
is a heater.
Claims (4)
級または第３級ホスファイトエステルとを含むことを特
徴とする石油精製用汚れ防止剤。(1) a styrene-maleic ester copolymer and a second
An antifouling agent for petroleum refining, characterized in that it contains a phosphite ester or a tertiary phosphite ester.
直鎖もしくは分岐アルキル基またはアルケニル基、ｍ：
ｎ（モル比）＝１：９〜９：１である。） で表わされる分子量１０，０００〜１，０００，０００
のものである特許請求の範囲第１項記載の汚れ防止剤。(2) The styrene-maleate ester copolymer has the following formula ▲ Numerical formulas, chemical formulas, tables, etc. Alkenyl group, m:
n (molar ratio) = 1:9 to 9:1. ) Molecular weight 10,000 to 1,000,000
The antifouling agent according to claim 1, which is an antifouling agent.
くは分岐アルキル基またはアルケニル基、Ｒ＿２、Ｒ＿
３は炭素数８〜１８の直鎖もしくは分岐アルキル基また
はアルケニル基である。） で表わされる分子量３００〜６００のものである特許請
求の範囲第１項または第２項記載の汚れ防止剤。(3) The secondary or tertiary phosphite ester has the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ... [II] (However, R_1 is hydrogen or a straight chain or branched alkyl group having 8 to 18 carbon atoms. or alkenyl group, R_2, R_
3 is a straight chain or branched alkyl group or alkenyl group having 8 to 18 carbon atoms. ) The antifouling agent according to claim 1 or 2, which has a molecular weight of 300 to 600.
比）が１：９〜９：１である特許請求の範囲第１項ない
し第３項のいずれかに記載の汚れ防止剤。(4) The antifouling agent according to any one of claims 1 to 3, wherein the blending ratio (weight ratio) of the copolymer and phosphite ester is 1:9 to 9:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5497387A JPS63221185A (en) | 1987-03-10 | 1987-03-10 | Contamination inhibitor used in petroleum refining |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5497387A JPS63221185A (en) | 1987-03-10 | 1987-03-10 | Contamination inhibitor used in petroleum refining |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63221185A true JPS63221185A (en) | 1988-09-14 |
Family
ID=12985596
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5497387A Pending JPS63221185A (en) | 1987-03-10 | 1987-03-10 | Contamination inhibitor used in petroleum refining |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63221185A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018207708A1 (en) * | 2017-05-09 | 2018-11-15 | 株式会社片山化学工業研究所 | Method for preventing fouling of heat exchanger in petroleum process |
| WO2021152718A1 (en) * | 2020-01-29 | 2021-08-05 | 株式会社片山化学工業研究所 | Method for preventing fouling of heat exchanger in petroleum processing |
-
1987
- 1987-03-10 JP JP5497387A patent/JPS63221185A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018207708A1 (en) * | 2017-05-09 | 2018-11-15 | 株式会社片山化学工業研究所 | Method for preventing fouling of heat exchanger in petroleum process |
| JP6485598B1 (en) * | 2017-05-09 | 2019-03-20 | 株式会社片山化学工業研究所 | Methods for preventing contamination of heat exchangers in petroleum processes. |
| WO2021152718A1 (en) * | 2020-01-29 | 2021-08-05 | 株式会社片山化学工業研究所 | Method for preventing fouling of heat exchanger in petroleum processing |
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