JPH0699695B2 - Method for removing lead compounds from liquid hydrocarbons - Google Patents
Method for removing lead compounds from liquid hydrocarbonsInfo
- Publication number
- JPH0699695B2 JPH0699695B2 JP17041191A JP17041191A JPH0699695B2 JP H0699695 B2 JPH0699695 B2 JP H0699695B2 JP 17041191 A JP17041191 A JP 17041191A JP 17041191 A JP17041191 A JP 17041191A JP H0699695 B2 JPH0699695 B2 JP H0699695B2
- Authority
- JP
- Japan
- Prior art keywords
- lead
- lead compounds
- adsorbent
- liquid hydrocarbons
- removing lead
- 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 - Lifetime
Links
- 150000002611 lead compounds Chemical class 0.000 title claims description 18
- 229930195733 hydrocarbon Natural products 0.000 title claims description 16
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 16
- 239000007788 liquid Substances 0.000 title claims description 15
- 238000000034 method Methods 0.000 title claims description 11
- 239000003463 adsorbent Substances 0.000 claims description 15
- 239000004215 Carbon black (E152) Substances 0.000 claims description 9
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- MRMOZBOQVYRSEM-UHFFFAOYSA-N tetraethyllead Chemical compound CC[Pb](CC)(CC)CC MRMOZBOQVYRSEM-UHFFFAOYSA-N 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 4
- 239000003498 natural gas condensate Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- UOFGSWVZMUXXIY-UHFFFAOYSA-N 1,5-Diphenyl-3-thiocarbazone Chemical compound C=1C=CC=CC=1N=NC(=S)NNC1=CC=CC=C1 UOFGSWVZMUXXIY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- -1 nickel sulfides molybdenum oxide Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- XOOGZRUBTYCLHG-UHFFFAOYSA-N tetramethyllead Chemical compound C[Pb](C)(C)C XOOGZRUBTYCLHG-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は鉛化合物を含有する液状
炭化水素中の鉛を除去する方法に関するものである。四
エチル鉛などの鉛化合物は、かつてガソリンのオクタン
価向上剤として広く使用されていたが、自動車エンジン
排ガスによる大気汚染の問題から使用されないようにな
った。それに伴い、鉛化合物を添加したハイオクタンガ
ソリン用として使用されていたタンクをナフサや天然ガ
スコンデンセートなどの液状炭化水素用タンクとして転
用すると、そのようなタンクに残留している四エチル鉛
が液状炭化水素に微量混入するため、その液状炭化水素
を石油化学原料として使用した場合、貴金属（Pt，Pd
等）系の触媒の劣化の原因となる。FIELD OF THE INVENTION The present invention relates to a method for removing lead in a liquid hydrocarbon containing a lead compound. Lead compounds such as tetraethyl lead were once widely used as an octane number improver for gasoline, but they are not used because of the problem of air pollution caused by automobile engine exhaust gas. Along with that, when the tank used for high octane gasoline with lead compounds added is converted to a tank for liquid hydrocarbons such as naphtha and natural gas condensate, the tetraethyl lead remaining in such tanks becomes liquid carbonized. Since a small amount of hydrogen is mixed with hydrogen, when the liquid hydrocarbon is used as a petrochemical raw material, the precious metal (Pt, Pd
Etc.) causes deterioration of the system catalyst.
【０００２】[0002]
【従来の技術】オクタン価向上剤として使用される鉛化
合物は天然物に由来する液状炭化水素中には本来存在し
ないものなので、液状炭化水素からの除去対象物として
扱われた事例は見当たらない。2. Description of the Related Art Since lead compounds used as octane number improvers do not exist naturally in liquid hydrocarbons derived from natural products, no cases have been found to be treated as objects to be removed from liquid hydrocarbons.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、上記のよう
に、特殊なケースとして生成した鉛化合物を含有する液
状炭化水素中の鉛化合物を除去する方法を提供すること
を目的とする。鉛化合物の具体例としては、四エチル鉛
又は四メチル鉛を挙げることができる。SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for removing lead compounds in a liquid hydrocarbon containing lead compounds produced as a special case as described above. Specific examples of the lead compound include tetraethyl lead and tetramethyl lead.
【０００４】[0004]
【課題を解決するための手段】本発明に関わる液状炭化
水素中の鉛化合物の除去方法は、鉛化合物を含有する液
状炭化水素を、モリブデンの硫化物を含有する吸着剤に
接触させることを特徴とする。The method for removing lead compounds in a liquid hydrocarbon according to the present invention is characterized in that a liquid hydrocarbon containing a lead compound is brought into contact with an adsorbent containing a sulfide of molybdenum. And
【０００５】モリブデンの硫化物は極めて高い鉛化合物
吸着活性を有しているが、モリブデンの硫化物による鉛
化合物の吸着効果を更に向上させるためには、コバルト
及び／又はニッケルと組み合わせ複合硫化物として用い
るのが有効である。コバルト及び／又はニッケルはモリ
ブデンの酸化物を硫化する際に、より低温で硫化を開始
させると同時に、コバルト及び／又はニッケルがモリブ
デンの硫化物の結晶にとりこまれてそのシンタリングが
防止され、その結果高分散の硫化物が得られるという効
果を与える。コバルト及び／又はニッケルの含有量はモ
リブデン１原子に対して０．０５〜０．９原子、好まし
くは０．１〜０．８原子であることが望ましい。原子比
０．０５以下では分散化の効果が小さく、一方０．９以
上に増しても効果はそれほど上がらない。Molybdenum sulfide has an extremely high activity of adsorbing lead compounds, but in order to further improve the adsorption effect of lead compounds by molybdenum sulfide, it should be combined with cobalt and / or nickel as a composite sulfide. It is effective to use. When cobalt and / or nickel sulfides molybdenum oxide, it starts sulfide at a lower temperature, and at the same time, cobalt and / or nickel is incorporated into the molybdenum sulfide crystal to prevent its sintering. As a result, it is possible to obtain a highly dispersed sulfide. The content of cobalt and / or nickel is 0.05 to 0.9 atom, preferably 0.1 to 0.8 atom per 1 atom of molybdenum. If the atomic ratio is 0.05 or less, the effect of dispersion is small, while if it is increased to 0.9 or more, the effect does not increase so much.
【０００６】これら金属の硫化物はそのままで吸着剤と
して用いることもできるが、吸着剤を担体に担持させて
用いると、吸着剤の分散度が向上し、単に吸着量を増加
させるのみならず、吸着速度も増加し、鉛化合物を有効
に除去できるので、担体に坦持させて用いるのが好まし
い。These metal sulfides can be used as an adsorbent as they are, but when the adsorbent is carried on a carrier, the dispersibility of the adsorbent is improved and not only the adsorption amount is increased, Since the adsorption rate is also increased and the lead compound can be effectively removed, it is preferable to use it by supporting it on a carrier.
【０００７】担体としては、シリカ、アルミナ、シリカ
−アルミナ、ゼオライト、セラミック、ガラス、樹脂又
は活性炭などを用いることができるが、特にアルミナに
吸着させた吸着剤は分散性が高く、本発明の吸着剤とし
て優れている。アルミナの中では特にγ−アルミナが好
適である。As the carrier, silica, alumina, silica-alumina, zeolite, ceramics, glass, resin, activated carbon or the like can be used. In particular, the adsorbent adsorbed on alumina has a high dispersibility, and thus the adsorbent of the present invention can be used. Excellent as an agent. Of the alumina, γ-alumina is particularly preferable.
【０００８】担体は比表面積が大きいものの方が接触効
率が良くなるので好ましく、５〜４００ｍ2 ／ｇ、特に
１００〜２５０ｍ2 ／ｇの比表面積を有するものが好ま
しいが、これらに限定されるものではない。[0008] What support preferably so better things large specific surface area the better the contact efficiency, 5~400m 2 / g, particularly preferably those having a specific surface area of 100 to 250 m 2 / g, which is limited to is not.
【０００９】担体に担持させる場合、モリブデンの硫化
物の担持量は金属として１〜２０ｗｔ％、特に５〜１５
ｗｔ％の範囲が好ましい。担持量がこれ以上になると担
体の効果が小さく分散が悪くなる。また担持量が少ない
場合には吸着剤あたりの吸着量が小さくなる。コバルト
及び／又はニッケルを添加した場合、その添加量は吸着
剤に対して金属として０．１〜５ｗｔ％であることが好
ましい。また吸着剤は他の金属成分又は無機成分を含ん
でいても差支えない。When supported on a carrier, the supported amount of molybdenum sulfide is 1 to 20 wt% as metal, especially 5 to 15%.
A range of wt% is preferred. If the amount supported is greater than this, the effect of the carrier is small and the dispersion becomes poor. Further, when the supported amount is small, the adsorbed amount per adsorbent becomes small. When cobalt and / or nickel is added, the addition amount is preferably 0.1 to 5 wt% as a metal with respect to the adsorbent. Further, the adsorbent may include other metal components or inorganic components.
【００１０】吸着温度は室温〜２７０℃、好ましくは室
温〜１００℃で、原料炭化水素が液状を保つ圧力条件下
で行う。The adsorption temperature is room temperature to 270.degree. C., preferably room temperature to 100.degree.
【００１１】鉛化合物を含有する液状炭化水素と吸着剤
との接触方法は任意であるが、特に固定床流通方式が好
ましい。固定床流通方式を採用することにより連続運転
が可能となる。The method of contacting the liquid hydrocarbon containing the lead compound with the adsorbent is arbitrary, but the fixed bed flow system is particularly preferable. Continuous operation is possible by adopting the fixed bed distribution method.
【００１２】本発明方法によれば、四エチル鉛等の混入
した液状炭化水素、例えば、ガソリン、灯油、軽油、直
留ナフサ、減圧留出油等の原油又は天然ガスコンデンセ
ート留分、熱分解ガソリン、接触分解ナフサ等の分解生
成油、天然ガスコンデンセート中の鉛化合物を効率よく
除去することができる。According to the method of the present invention, liquid hydrocarbons mixed with tetraethyl lead or the like, for example, crude oil such as gasoline, kerosene, light oil, straight run naphtha, vacuum distillate or natural gas condensate fraction, pyrolysis gasoline It is possible to efficiently remove cracked oil such as catalytically cracked naphtha and lead compounds in natural gas condensate.
【００１３】以下実施例により本発明を具体的に説明す
る。The present invention will be specifically described with reference to the following examples.
【００１４】[0014]
【実施例１及び２】東南アジア産天然ガスコンデンセー
トを原料としたフルレンジナフサ（沸点範囲：３０〜１
６５℃）に四エチル鉛を９９．８ｐｐｂ（ｗｔ）及び３
９６ｐｐｂ（ｗｔ）添加したものを試料として吸着剤に
よる鉛除去処理を行った。試料炭化水素１５０ｍｌと４
０〜６０メッシュに揃えたNi・Co・Mo・S吸着剤（Ni：０．
５ｗｔ％，Co：０．９ｗｔ％，Mo：７．０ｗｔ％，担
体：γ−アルミナ）１５０ｍｇをガラス製容器にとって
密閉し振とう機を用いて室温で６０分間激しく振とうし
た。静置後、炭化水素を分離し、ジチゾン吸光光度法に
より鉛濃度を測定した。本方法による定量下限は２ｐｐ
ｂ（ｗｔ）である。実験結果は下記の通りで、ナフサ中
の四エチル鉛をほとんど除去することができ、除去率は
９８％以上の結果を得た。 試料中Pb濃度 処理液中Pb濃度 除去率 実施例１ 99.8 ppb(wt) ＜2 ppb(wt) ＞98 ％ 実施例２ 396 ppb(wt) ＜2 ppb(wt) ＞99.5％[Examples 1 and 2] Full-range naphtha (boiling range: 30 to 1) using Southeast Asian natural gas condensate as a raw material
99.8 ppb (wt) of tetraethyl lead and 3 at 65 ° C)
The sample to which 96 ppb (wt) had been added was used as a sample, and a lead removal process was performed using an adsorbent. Sample hydrocarbon 150ml and 4
Ni ・ Co ・ Mo ・ S adsorbents (Ni: 0.
150 mg of 5 wt%, Co: 0.9 wt%, Mo: 7.0 wt%, carrier: γ-alumina) was sealed in a glass container and vigorously shaken at room temperature for 60 minutes using a shaker. After standing, the hydrocarbons were separated and the lead concentration was measured by the dithizone absorptiometry. The lower limit of quantification by this method is 2 pp
b (wt). The experimental results are as follows, and almost all tetraethyl lead in naphtha was removed, and the removal rate was 98% or more. Pb concentration in the sample Pb concentration in the treated solution Removal rate Example 1 99.8 ppb (wt) <2 ppb (wt)> 98% Example 2 396 ppb (wt) <2 ppb (wt)> 99.5%
【００１５】[0015]
(1) 吸着工程だけで液状炭化水素中の鉛化合物を除去で
きるため、シンプルなプロセスとなる。 (2) 常温、常圧で運転できる。 (3) 吸着剤は安価である。 (4) 吸着剤は安定化合物であり、ハンドリングが容易で
ある。(1) Since the lead compound in the liquid hydrocarbon can be removed only by the adsorption step, the process is simple. (2) It can be operated at room temperature and pressure. (3) The adsorbent is inexpensive. (4) The adsorbent is a stable compound and easy to handle.
Claims (1)
リブデンの硫化物を含有する吸着剤に接触させることを
特徴とする液状炭化水素中の鉛化合物の除去方法。1. A method for removing lead compounds from liquid hydrocarbons, which comprises contacting a liquid hydrocarbon containing a lead compound with an adsorbent containing a sulfide of molybdenum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17041191A JPH0699695B2 (en) | 1991-06-17 | 1991-06-17 | Method for removing lead compounds from liquid hydrocarbons |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17041191A JPH0699695B2 (en) | 1991-06-17 | 1991-06-17 | Method for removing lead compounds from liquid hydrocarbons |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04371207A JPH04371207A (en) | 1992-12-24 |
| JPH0699695B2 true JPH0699695B2 (en) | 1994-12-07 |
Family
ID=15904430
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17041191A Expired - Lifetime JPH0699695B2 (en) | 1991-06-17 | 1991-06-17 | Method for removing lead compounds from liquid hydrocarbons |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0699695B2 (en) |
-
1991
- 1991-06-17 JP JP17041191A patent/JPH0699695B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04371207A (en) | 1992-12-24 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 19950606 |