JPS6310197B2 - - Google Patents
Info
- Publication number
- JPS6310197B2 JPS6310197B2 JP54106613A JP10661379A JPS6310197B2 JP S6310197 B2 JPS6310197 B2 JP S6310197B2 JP 54106613 A JP54106613 A JP 54106613A JP 10661379 A JP10661379 A JP 10661379A JP S6310197 B2 JPS6310197 B2 JP S6310197B2
- Authority
- JP
- Japan
- Prior art keywords
- sludge
- polyethylene glycol
- petroleum
- acid ester
- glycol monofatty
- 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.)
- Expired
Links
- 239000010802 sludge Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 13
- 239000003208 petroleum Substances 0.000 claims description 13
- 239000002202 Polyethylene glycol Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
- 238000009825 accumulation Methods 0.000 claims description 9
- 230000008021 deposition Effects 0.000 claims description 5
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- 125000005313 fatty acid group Chemical group 0.000 claims 1
- 239000010779 crude oil Substances 0.000 description 11
- 239000003921 oil Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000012188 paraffin wax Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Liquid Carbonaceous Fuels (AREA)
Description
本発明は石油スラツジの堆積防止方法に関し、
とくに原油スラツジの堆積防止方法に関する。
現在わが国で最も多く使用されているエネルギ
ー源である石油はほとんどすべて海外から輸入さ
れ、巨大なタンクに貯蔵される。このタンクの大
きさをみると１基10万Ｋ以上の超大型タンクが
全体の４割弱を占め、平均約６万Ｋである。
一方、エネルギー供給の安定化を計る目的で石
油の長期備蓄計画が進められているが、この計画
に用いられるタンクはさらに巨大なものになると
考えられる。
石油、とくに原油を貯蔵する場合に大きな問題
となつているのは、各種の安全対策とともにタン
ク底部に堆積するスラツジの問題である。
容量10万Ｋのタンクの場合、タンク底から数
ｍの高さまでスラツジが堆積しているタンクもあ
り、そのスラツジ量は１万Ｋ以上に達する。
スラツジの堆積はタンクの実質的な貯蔵能力を
低下させるばかりではなく、タンクに付属する送
油管やポンプ等を閉塞する原因となる。
このスラツジは分子量の大きなパラフイン類が
主成分となり、これに芳香族高分子化合物、アス
フアルテン、レジン、水等が混合した複雑な組成
をとるもので、流動点が非常に高いためにその除
去に多大な経費を必要とする。
このようなことは原油に限らず重油タンクでも
起こり、石油を大量に消費する発電所等の事業所
でも重要な問題となつている。
このスラツジの堆積を防止する方法として現在
わが国で行われている方法はもつぱら機械的な方
法である。すなわち、タンクの側面につけた撹拌
機によつてタンク内の原油を強制的に対流させ、
スラツジが沈降するのを防ぐ方法である。しか
し、巨大なタンクではタンク内の一部に流れが生
じるだけで充分な効果が得られない。また、撹拌
機の運転に要する電力も無視できず、とくに長期
備蓄用のタンクでは経済的に不利である。
これらの理由から、微量の化学物質を添加して
スラツジの堆積を防止する方法が検討されるよう
になり、米国ではかなり以前から検討されてき
た。
その方法はスラツジの成分であるパラフイン等
の結晶が析出するのを防止することを目的として
いる。しかし、この方法をわが国の場合にあては
めることはできない。わが国に輸入される原油
は、気温のかなり高い中東等の遠隔地から長期間
かけて比較的冷涼なわが国まで運ばれてくるた
め、輸入原油中には充分に析出し、かつ成長した
パラフイン等の結晶がすでに存在しているからで
ある。
以上の理由から、本発明者等はわが国の石油事
情に合致したスラツジの堆積防止方法として、す
でに最大限に近く発生しているスラツジを界面活
性物質によつて石油中に安定に分散させ、タンク
底に沈降させないようにする目的で検討を積み重
ねた結果、石油にポリエチレングリコールモノ脂
肪酸エステルを添加することによりスラツジの堆
積が有効に防止されることを見いだした。
本発明で使用するポリエチレングリコールモノ
脂肪酸エステルは炭素数８〜18の飽和または不飽
和の脂肪酸にエチレンオキシドを２〜40モル付加
したものであり、HLB値が８〜20のものが石油
スラツジの堆積防止用として好ましく使用でき
る。
ここで、原料となる炭素数８〜18の脂肪酸とし
ては、たとえばカプリン酸、ラウリン酸、ミリス
チン酸、パルミチン酸、ステアリン酸、オレイン
酸、リノール酸、イソステアリン酸、２−エチル
ヘキサン酸などがある。
これらポリエチレングリコールモノ脂肪酸エス
テルは石油に対し２〜500ppm、好ましくは５〜
150ppmを添加する。2ppm未満では効果が小さ
く、500ppm以上では経済的に不利である。
本発明で使用するポリエチレングリコールモノ
脂肪酸エステルは、原料脂肪酸のアルキル基の長
さや構造およびエチレンオキシドの付加量等で規
定されるHLB値によつて、石油スラツジの堆積
防止効果に差があるが、石油の種類によつてこれ
らの条件を適切に選ぶことにより、スラツジの堆
積量を非常に少なくすることができる。
一方、パラフイン析出防止剤である分枝ポリエ
チレン（米国特許第3640824号）やナフタレン
（米国特許第3276519号）を用いた場合には堆積ス
ラツジ量はほとんど減少せず、何も添加しない場
合との差はほとんど認められなかつた。
しかし、原油を長期にわたつて備蓄する場合、
徐々に新たなパラフイン等の結晶が析出するとき
にはこれらのパラフイン析出防止剤と本発明のポ
リエチレングリコールモノ脂肪酸エステルを併用
すると効果的であろう。
つぎに本発明を実施例および比較例によつて説
明するが、試験はつぎの方法で行つた。
試験容器として100ml遠沈管（JIS Ｋ−2603−
1971 遠心分離用Ｉ型目盛試験管）を使用し、こ
れに原油を100mlとり、つぎに添加剤を加えたの
ち、密栓して振とう混合したものを所定温度で静
置した。所定期間経過したのち、この遠沈管を逆
さにして原油を流し出し、逆さにしたままさらに
１時間同じ恒温室中に静置した。この状態でまだ
底部に残つている堆積スラツジの量を遠心管目盛
で読みとり、堆積防止効果を判断した。
表−１はバスラライト原油を用い、20℃で100
日間静置した場合の試験結果であるが、本発明の
ポリエチレングリコールモノ脂肪酸エステルを添
加した実施例１〜８は堆積スラツジ量が少いこと
が明らかである。比較例１は添加剤を加えない場
合、比較例２と３は前記米国特許のパラフイン析
出防止剤を加えた場合である。
The present invention relates to a method for preventing the accumulation of petroleum sludge,
In particular, it relates to a method for preventing accumulation of crude oil sludge. Oil, the most commonly used energy source in Japan today, is almost entirely imported from overseas and stored in huge tanks. Looking at the size of these tanks, just under 40% of them are ultra-large tanks with a capacity of 100,000K or more each, and the average capacity is about 60,000K. Meanwhile, a long-term oil stockpiling plan is underway to stabilize energy supplies, but the tanks used in this plan are likely to be even larger. A major problem when storing oil, especially crude oil, is the problem of sludge accumulating at the bottom of tanks, as well as various safety measures. In some tanks with a capacity of 100,000K, sludge accumulates several meters from the bottom of the tank, and the amount of sludge reaches over 10,000K. The accumulation of sludge not only reduces the actual storage capacity of the tank, but also causes blockage of oil pipes, pumps, etc. attached to the tank. This sludge has a complex composition consisting mainly of large-molecular-weight paraffins, mixed with aromatic polymer compounds, asphaltene, resin, water, etc. Because it has a very high pour point, it takes a lot of effort to remove it. It requires a large amount of expenses. This kind of thing occurs not only in crude oil tanks but also in heavy oil tanks, and has become an important problem in business establishments such as power plants that consume large amounts of oil. The methods currently used in Japan to prevent the accumulation of sludge are exclusively mechanical methods. In other words, a stirrer attached to the side of the tank forces convection of the crude oil in the tank.
This is a method to prevent sludge from settling. However, in a huge tank, the flow only occurs in a part of the tank and the effect is not sufficient. Furthermore, the electric power required to operate the stirrer cannot be ignored, which is economically disadvantageous, especially in tanks for long-term storage. For these reasons, methods of adding small amounts of chemicals to prevent sludge buildup have been studied in the United States for quite some time. The purpose of this method is to prevent the precipitation of crystals such as paraffin, which is a component of the sludge. However, this method cannot be applied to the case of Japan. Crude oil imported into Japan is transported from remote areas such as the Middle East, where the temperature is quite high, to Japan, where it is relatively cool, over a long period of time. This is because crystals already exist. For the above reasons, the present inventors have developed a method for preventing the accumulation of sludge that is consistent with Japan's petroleum situation by stably dispersing the sludge, which has already been generated close to the maximum, into oil using a surfactant. As a result of repeated studies aimed at preventing sludge from settling to the bottom, it was discovered that adding polyethylene glycol monofatty acid ester to petroleum can effectively prevent the accumulation of sludge. The polyethylene glycol monofatty acid ester used in the present invention is a saturated or unsaturated fatty acid having 8 to 18 carbon atoms added with 2 to 40 moles of ethylene oxide, and those with an HLB value of 8 to 20 are effective in preventing the accumulation of petroleum sludge. It can be preferably used for Here, examples of fatty acids having 8 to 18 carbon atoms as raw materials include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, isostearic acid, and 2-ethylhexanoic acid. These polyethylene glycol monofatty acid esters are 2 to 500 ppm, preferably 5 to 500 ppm based on petroleum.
Add 150ppm. If it is less than 2 ppm, the effect is small, and if it is more than 500 ppm, it is economically disadvantageous. The polyethylene glycol monofatty acid ester used in the present invention has a different effect on preventing petroleum sludge deposition depending on the length and structure of the alkyl group of the raw fatty acid and the HLB value defined by the amount of ethylene oxide added. By appropriately selecting these conditions depending on the type of sludge, the amount of sludge deposited can be extremely reduced. On the other hand, when branched polyethylene (U.S. Pat. No. 3,640,824) or naphthalene (U.S. Pat. No. 3,276,519), which are paraffin precipitation inhibitors, are used, the amount of deposited sludge hardly decreases, and there is no difference from the case where nothing is added. was hardly recognized. However, when storing crude oil for a long period of time,
When new crystals such as paraffin are gradually precipitated, it may be effective to use these paraffin precipitation inhibitors in combination with the polyethylene glycol monofatty acid ester of the present invention. Next, the present invention will be explained with reference to Examples and Comparative Examples, and tests were conducted in the following manner. A 100ml centrifuge tube (JIS K-2603-
Using a Type I graduated test tube for centrifugation (1971), 100 ml of crude oil was added, and then additives were added, the mixture was tightly capped and shaken, and the mixture was allowed to stand at a predetermined temperature. After a predetermined period of time had elapsed, the centrifuge tube was turned upside down, the crude oil was poured out, and the tube was left standing upside down in the same constant temperature room for another hour. In this state, the amount of accumulated sludge still remaining at the bottom was read using a centrifuge tube scale to determine the effect of preventing accumulation. Table 1 uses basralite crude oil at 100°C at 20°C.
The test results obtained when the samples were allowed to stand for one day showed that Examples 1 to 8 in which the polyethylene glycol monofatty acid ester of the present invention was added had a small amount of deposited sludge. Comparative Example 1 is a case in which no additive is added, and Comparative Examples 2 and 3 are cases in which the above-mentioned US patent paraffin precipitation inhibitor is added.
【表】
表−２はウムシヤイフ原油を用い、20℃で100
日間静置した場合を示すが、本発明のポリエチレ
ングリコールモノ脂肪酸エステルを使用した実施
例10〜16は、いずれも堆積スラツジの量が著しく
少なかつた。[Table] Table-2 uses Umm-Syaif crude oil, and
In Examples 10 to 16, in which the polyethylene glycol monofatty acid ester of the present invention was used, the amount of deposited sludge was significantly small.
【表】
表−３はマーバン原油を用い20℃で100日間静
置した場合の試験結果であるが、本発明の実施例
17〜23はいずれも良好な堆積防止効果を示した。[Table] Table 3 shows the test results when Murban crude oil was left standing at 20℃ for 100 days.
Nos. 17 to 23 all showed good anti-deposition effects.
Claims (1)
ステルを添加することを特徴とする石油スラツジ
の堆積防止方法。 ２ ポリエチレングリコールモノ脂肪酸エステル
が炭素数８〜18の脂肪酸から誘導したものである
特許請求の範囲第１項記載の石油スラツジの堆積
防止方法。 ３ ポリエチレングリコールモノ脂肪酸エステル
が脂肪酸にエチレンオキシドを２〜40モル付加し
たものである特許請求範囲第１項または第２項記
載の石油スラツジの堆積防止方法。 ４ ポリエチレングリコールモノ脂肪酸エステル
のHLB値が８〜20である特許請求の範囲第１項、
第２項または第３項記載の石油スラツジの堆積防
止方法。 ５ ポリエチレングリコールモノ脂肪酸エステル
の添加量が石油に対して２〜500ppmである特許
請求の範囲第１項、第２項、第３項または第４項
記載の石油スラツジの堆積防止方法。[Claims] 1. A method for preventing deposition of petroleum sludge, which comprises adding polyethylene glycol monofatty acid ester to petroleum. 2. The method for preventing deposition of petroleum sludge according to claim 1, wherein the polyethylene glycol monofatty acid ester is derived from a fatty acid having 8 to 18 carbon atoms. 3. The method for preventing deposition of petroleum sludge according to claim 1 or 2, wherein the polyethylene glycol monofatty acid ester is a fatty acid with 2 to 40 moles of ethylene oxide added thereto. 4 Claim 1, wherein the polyethylene glycol monofatty acid ester has an HLB value of 8 to 20;
The method for preventing accumulation of petroleum sludge according to item 2 or 3. 5. The method for preventing deposition of petroleum sludge according to claim 1, 2, 3, or 4, wherein the amount of polyethylene glycol monofatty acid ester added is 2 to 500 ppm based on petroleum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10661379A JPS5630494A (en) | 1979-08-23 | 1979-08-23 | Prevention of deposition of petroleum sludge |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10661379A JPS5630494A (en) | 1979-08-23 | 1979-08-23 | Prevention of deposition of petroleum sludge |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5630494A JPS5630494A (en) | 1981-03-27 |
| JPS6310197B2 true JPS6310197B2 (en) | 1988-03-04 |
Family
ID=14437963
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10661379A Granted JPS5630494A (en) | 1979-08-23 | 1979-08-23 | Prevention of deposition of petroleum sludge |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5630494A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5355305A (en) * | 1976-10-28 | 1978-05-19 | Dai Ichi Kogyo Seiyaku Co Ltd | Additive for finely powdered coal and oil mixture |
| JPS5452106A (en) * | 1977-10-03 | 1979-04-24 | Dai Ichi Kogyo Seiyaku Co Ltd | Additive for pulverized coal-oil mixtures |
-
1979
- 1979-08-23 JP JP10661379A patent/JPS5630494A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5355305A (en) * | 1976-10-28 | 1978-05-19 | Dai Ichi Kogyo Seiyaku Co Ltd | Additive for finely powdered coal and oil mixture |
| JPS5452106A (en) * | 1977-10-03 | 1979-04-24 | Dai Ichi Kogyo Seiyaku Co Ltd | Additive for pulverized coal-oil mixtures |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5630494A (en) | 1981-03-27 |
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