CA2077705A1 - Process for the storage and transportation of liquid hydrocarbons - Google Patents
Process for the storage and transportation of liquid hydrocarbonsInfo
- Publication number
- CA2077705A1 CA2077705A1 CA 2077705 CA2077705A CA2077705A1 CA 2077705 A1 CA2077705 A1 CA 2077705A1 CA 2077705 CA2077705 CA 2077705 CA 2077705 A CA2077705 A CA 2077705A CA 2077705 A1 CA2077705 A1 CA 2077705A1
- Authority
- CA
- Canada
- Prior art keywords
- hydrocarbon
- gel
- surfactant
- transportation
- rich
- 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.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L7/00—Fuels produced by solidifying fluid fuels
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T137/00—Fluid handling
- Y10T137/0318—Processes
- Y10T137/0324—With control of flow by a condition or characteristic of a fluid
- Y10T137/0329—Mixing of plural fluids of diverse characteristics or conditions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T137/00—Fluid handling
- Y10T137/0318—Processes
- Y10T137/0324—With control of flow by a condition or characteristic of a fluid
- Y10T137/0329—Mixing of plural fluids of diverse characteristics or conditions
- Y10T137/0335—Controlled by consistency of mixture
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T137/00—Fluid handling
- Y10T137/0318—Processes
- Y10T137/0391—Affecting flow by the addition of material or energy
Abstract
ABSTRACT
The present invention relates to the use of hydrocarbon-rich gels as a safe storage or transportation form for liquid hydrocarbons and to a process for the safe storage and safe transportation of liquid hydrocarbons. In the process according to the invention, the hydrocarbon is converted into a hydrocarbon-rich gel by addition of a surfactant and water. After storage or transportation has taken place, the hydrocarbon-rich gel is broken down again. The surfactant and water are preferably added to the hydrocarbon in amounts such that a hydrocarbon-rich gel of 70 to 99.5% by weight of hydrocarbon, 0.01 to 15% by weight of surfactant and 0.49 to 15% by weight of water is formed. The gels are distinguished by a flow limit, which means that although they can be pumped in a simple manner, they cannot flow in the state of rest and therefore cannot be accidentally discharged from defective storage or transportation tanks, thus considerably reducing environmental hazards due to storage or transportation of hydrocarbons.
The present invention relates to the use of hydrocarbon-rich gels as a safe storage or transportation form for liquid hydrocarbons and to a process for the safe storage and safe transportation of liquid hydrocarbons. In the process according to the invention, the hydrocarbon is converted into a hydrocarbon-rich gel by addition of a surfactant and water. After storage or transportation has taken place, the hydrocarbon-rich gel is broken down again. The surfactant and water are preferably added to the hydrocarbon in amounts such that a hydrocarbon-rich gel of 70 to 99.5% by weight of hydrocarbon, 0.01 to 15% by weight of surfactant and 0.49 to 15% by weight of water is formed. The gels are distinguished by a flow limit, which means that although they can be pumped in a simple manner, they cannot flow in the state of rest and therefore cannot be accidentally discharged from defective storage or transportation tanks, thus considerably reducing environmental hazards due to storage or transportation of hydrocarbons.
Description
2~7~7~
Ref. 3481 D~.My/asO075 Process for the storaae and transportation of liquid hydrocarbons The present invention relates to the use of hydrocarbon-rich gels as a safe storage and transportation form for liquidhydrocarbons and to a process for the safe storage and the safe transportation of liquid hydrocarbons, the hydrocarbon being converted into a hydrocarbon-rich gel which is broken down again after storage or transportation.
The storage and transportion of liquid hydrocarbons, for example fuels, via roads, rail and on the waterways present a considerable potential hazard. Thus, for example, the high flamm-ability and explosiveness in mixtures of air has led in the past to serious accidents which have caused considerable damage.
Serious ecological damage moreover constantly results from fuels discharged from leaking storage or transportation tanks.
The ob~ect of the present invention is therefore to provide a process for the safe storage and the safe transporta-tion of hydrocarbons.
This ob~ect is achieved, surprisingly, by storing and transporting the hydrocarbons in the form of hydrocarbon-rich gel~.
A hydrocarbon-rich gel is under~tood as meaning a system which consist~ of polyhedrons which are formed from surfactant and are filled with hydrocarbon, water forming a continuous phase in the narrow interstices between the polyhedron~. Systems of this type are known and are described in Angew. Chem. 100 933 (1988) and Ber. Bun~enge~. Phys. Chem. 92 1158 (1988).
Hydrocarbon-rich gels are distinguished by the occurrence of a flow limit. This flow limit is reached when the gel no longer withstand~ a stress imposed on it (shear, deformation) and starts to flow. Below the flow limit, the gel ~tructures have the properties of solid~ and obèy Hooke~s law. Above the flow limit, in the ideal case, the sy~tem is equivalent to a Newtonian fluid.
This means that although hydrocarbon-rich gel~ can be pumped in a simple manner, they cannot flow in the state of re~t because of their properties of solids. They therefore cannot be discharged from defective storage or transportation tanks, and danger to the en~ironment is virtually excluded.
2~777~
The present invention thus relates to the use of hydro-~ bon-rich gels as a safe s~orage and transportation form for liquid hydrocarbons.
The present invention furthermore relates to a process for the safe storage and the safe transportation of liquld hydro-carbons, characterised in that a) the hydrocarbon is converted into a hydrocarbon-rich gel by addition of a surfactant and water and b) after storage or transportation has taken place, the hydro-carbon-rich gel is broken down again.
The surfactant and water are preferably added to the hydrocarbon in amounts such that a hydrocarbon-rich gel of 70 to 99.5% by weight of hydrocarbon, 0.01 to 15% by weight of surfac-tant and 0.49 to 15~ by weight of water is formed.
The surfactant and water are particularly preferably added to the hydrocarbon in amounts such that a hydrocarbon-rich gel of 80 to 99.5% by weight of hydrocarbon, 0.01 to 5% by weight of surfactant and 0.49 to 15% by weight of water is formed.
Hydrocarbons which are particularly suitable for the process according to the invention are n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-dodecane, n-tetradecane, n-hexadecane, cyclohexane, cyclooctane, benzene, toluene, kerosene, petrol, lead-free petrol, heating oil, diesel oil and crude oil.
Anionic, cationic, amphoteric or non-ionic surfactants can be employed to form the hydrocarbon-rich gel-q.
Preferred anionic surfactantc are soaps of the formula R-CH2-COOqNa~
wherein R denotes a hydrocarbon radical having 10 to 20 C atoms;
alkanesulphonates of the fo mula CH--S03/3Na R ' wherein R and R' denote al~yl radicals having together 11 to 17 C atom~;
2~777~5 alkylbenzenesulphonates and -sulfates of the formula R / ~3~ ) n--SO3 Na wherein n is O or 1 and R and R~ denote alkyl radicals having together 11 to 13 S C atoms;
olefinesulphonates of the formula R-CH2-CH = CH-CHz-SO3~Na~
wherein R denotes alkyl having 10 to 14 C atoms;
fatty alcohol sulphates of the formula R-CH2-O-SO3~
wherein R denotes alkyl having 11 to 15 C atoms and Y~ denotes Na~ or triethanolamine;
fatty alcohol polyglycol sulphates of the formula R-CH2-O ( C2H40 ) n-SO3eNa wherein n is 2 to 7 and R denotes alkyl having 8 to 15 C atoms;
sulphosuccinates of the formula 2 ( C2H4O ) n--C--ICH--CH COO Nd0 wherein n is 2 to 6 and R denote~ alkyl having 11 to 13 C atoms;
fatty alcohol polyglycol phosphates of the formula R-CH2-O(C2H4o)npo3HqNa wherein n i~ 2 to 6 and R denotes alkyl having 15 to 17 C atoms;
alkanephosphonates of the formula R-POaH~Na~
wherein R denotes alkyl having 12 to 16 C a~oms;
and ~odium salt~ of oleic acid derivatives, such as oleic acid sarcoside, oleic acid iso~hionate or oleic acid methyl-tauride.
2~7~7t~
Preferred cationic surfactants are aternary ammonium compounds of the formula R R~
N X
R~/ \R4 wherein R~ denotes alkyl having 10 to 22 C atoms, R2 denotes alkyl having 1 to 12 C atoms or benzyl, R3 and R4 independently of one another denote hydrogen or methyl and xe denotes Cle, Bre or CH3So49;
fatty amines, such as, for example, coconut-fatty amines, lauryl-fatty amine, oleyl-fatty amine, stearyl-fatty amine, tallow-fatty amine, dimethyl-fatty amines or primary alkylamines having pure chains of 8 to 22 C atoms;
ammonium borate betaine based on didecylamine;
stearyl-N-acylamido-N-methyl-imidazolinium chlorides of the formula ~C 1 7 H 3 S
H3C CH2CH2NHcl~cl7 35 cle and alkenyl~uccinic acid derivatives of the formulae Il - or o o 2 0GN N H N H N H N~R
wherein R in each case denotes i~o-C1~H3~ or polybutenyl.
Preferred amphoteric surfactants are, for example?~ 777 a. ~lbetaines of the formula wherein R denotes alkyl having 12 to 14 C atoms;
N-carboxyethyl-N-alkylamido-ethylglycinates of the formula R-l-NH-CH2-CH2- I H-CH?-COO
CH 7 - CH zOH
wherein R denotes alkyl having 11 to 13 C atoms; and N alkylamido-propyl-N-dimethylamine oxides of the formula R-C-NH-~CH2) -~
wherein R denotes alkyl having 11 to 13 C atoms.
Preferred non-ionic surfactants are, for example, 1,4-~orbitan fatty acid esters of the formula Hl_OH
H C~
HCOH
CH2 ~nc - R
wherein R denotes alkyl having 11 to 17 C atoms;
fatty alcohol polyglycol ethers of the formula R-O(CH2~CH2~o)nH
wherein n i~ 3 to 15 and R denotes straight-chain or branched alkyl having 9 to 19 C atom~; and . . .
alkylphenol polyglycol ethers of the formula 2 ~ 7 7 7 H- C ~ ~(CH2-CH2~~)n R' wherein n is 3 to 15 and R and R~ denote alkyl having together 7 to 11 C atoms.
S After storage or transportation has taken place, the lLquid hydrocarbon must be recovered again, that is to say the gel structure must be broken down.
This is preferably effected by treatment with mechanical waves, by application of a reduced pressure or vacuum or, if the hydrocarbon-rich gel is formed with the aid of an ionic surfac-tant, by addition of an oppositely charged substance.
Mechanical waves are understood as meaning, in particu-lar, high-frequency pressure waves, that is to say, for example, ultra~ound. When the gel tructure is broken down by ultrasound, the hydrocarbon phase already starts to emerge from the gel structure after only a few seconds. The separation has ended when two highly fluid phases are present side by side. This is as a N le the case after about 30 seconds.
If the gel structure is broken down by application of a reduced pressure or vacuum, the preferred range depends of course on the boiling point of the hydrocarbon. A vacuum of up to 0.1 torr is u~ually advantageous.
Oppositely charged surfactants or polymers or copolymers are preferably employed for breaking down gel structures formed with ionic surfactants.
In the ca~e where gel structures based on cationic sur-factants are broken down, the abovementioned anionic surfactants are particularly preferably employed.
Particularly preferred polymers having anionic groups are, for example, polyacrylates consisting of base elements of the formula --CH;?--~;H--COnH
which can also be crosslinked and/or completely or partly neutralised; ~7~7~5 poly-2-acylamido-2-methyl-propanesu~phonic acids consisting of base elements of the formula --C H ~--f H--C(~NH--C ( CH3 ) 2 C~2 ~i 3 S which can also be crosslinked and/or completely or partly neutra-lised;
or poly-vinylphosphonic acids consisting of base elements of the formula 2 f H
which can also be crosslinked and/or completely or partly neutra-lised.
Mixtures of the polymers mentioned or polymer~ which contain several of the base elements mentioned are also pre-ferred. Polymers which consist, for example, of the above-mentioned base elements having a negative charge and those havinga positive charge can also be employed.
Crosslinked, partly neutralised polyacrylic acid is especially preferred. This moreover has the advantage that, because of its enormous absorption jcapacity for water, it can bind quantitatively the aqueous phase of the gel to be broken down. Because of this absorption capacity for water, crosslinked, partly neutralised polyacrylic acid can break down not only gel structures based on cationic surfactants, but also those based on anionic, amphoteric or non-ionic surfactants.
2~ The abovementioned cationic surfactants are particularly preferably employed in the case of breaking down gel structures based on anionic surfactants.
Particularly preferred polymers having cationic groups are, for example poly-diallyl-dimethyl-ammonium chloride, which can also be cross-linked and/or completely or partly neutralised, or poly-methacrylic acid 2-dimethylaminoethyl ester, consisting of base elements of the formula ' 2 ~ 7 ~ 7 ~ ;~
--CH2~f ~ CH3 )-- CH~, which can also be crosslinked and/or completely or partly neutra-lised.
Mixtures of the polymers mentioned or polymers which contain both the base elements mentioned are also preferred.
Polyme~s which consist, for example, of the abovementioned base elements having a positive charge and those having a negative charge can also be employed.
The breaking down of the gel structure is carried out in a ~imple manner by adding the surfactant or polymer, as such or dissolved in a suitable solvent, to the gel structure and shaking the mixture briefly. The disintegration of the gel then starts ~pontaneously and is faster, the higher the counterion concentra-tion. Appropriate gel disintegration rates are in fact achieved, depending on the ~ystem, if 0.2 to ~5 g, preferably 0.4 to 5 g, of oppo~itely charged surfactant or polymer are added per g of surfactant contained in the gel.
Suitable solvents in which the surfactant or polymer employed for breakdown of the gel can be dissolved are, for example, xylene, water or alcohols.
The concentrations of the surfactants in the solvent~ are not critical, but are preferably from 30% by weight up to satura-tion of the solution. If the hydrocarbon to be stored or trans-ported is a fuel or lubricating oil, it is particularly advan-tageous if surfactants which can remain in the hydrocarbon as an additive are cho3en both for the gel formation and for the break-down of the gel.
For ex~mple, sulphonate~ are known as detergent additives and alkenylsuccinic acid imidoamines are known as dispersant additives (J. Raddatz, W.S. Bartz, 5. Int. Koll. 14. - 16.1.1986, Technische Akademie Esslingen ~dditive f~r Schmierstoffe und Arbeitsflussigkeiten tAdditives for lubricants and working fluids]'). Succinimides are also known as oil and fuel additives (see, for example, EP 198 690, US 4,614,603, EP 119 675, DE 3 814 601 or EP 295 789).
2~777~
EYample 1 a, Preparation 1 g of sodium dodecyl-sulphate was dissolved in 9 g of water and the solution was initially introduced into a wide-necked conical flask. 400 g of ligroin were added at roomtemperature, while stirring vigorously by means of a magnetic stirrer. A hydrocarbon-rich gel system was formed by this proce-dure.
b) Pumping experiments Pumping experiments were carried out with this gel system with the aid of an Ika tube pump. The diameter of the poly-ethylene tube used was 4 mm. The pumpability was recorded as the amount of gel pumped from vessel A to ves~el B after a defined unit of time. The mea3urement results from a duration of the experiment of 5 minutes at different pumping speeds are summar-ised below:
Speed level Duration of experiment Amount of gel pumped 5 minutes 3.8 g 5 minutes 3.7 g 5 minutes 4.4 g 5 minutes 4.1 g 5 minutes 2.9 g 5 minutes 3.8 g 5 minutes 3.9 g 5 minute~ 3.8 g 5 minute~ 4.4 g 5 minutes 4.3 g 5 minutes 4.3 g 5 minutes 4.5 g 5 minutes 4.2 g 5 minutes 4.5 g 5 minutes 3.8 g SummaJ~i~ing, it can be ~aid that, becauqe of the visco-elasticity of the gel ~ystems, the pump delivery proves to be independent of the pumping ~peed.
c) Storage and transportion 2 ~;3 7 r~ 7 ~ ~;
No changes in the consistency or rheological properties oi he gel system were to be found over an observation period of six months. A permanent shear or a violent shaking movement during transportation by rail and road has no influence on the stability of the gel.
d) Breakdown of the gel by ultrasound ln a series of experiments, 50 g of gel each time having the composition described under la were broken down using the Sonifier Cell Disruptor B-30 ultrasollnd unit, different energy 10 levels being set. The time of complete breakdown of the structure was recorded:
Energy level TLme to breakdown Level 10 1 second Level 8 10 seconds 15Level 6 35 seconds Level 4 197 seconds Level 3 390 seconds e) Breakdown of the gel by application of a vacuum 50 g of the gel prepared according to Example la in a 1 litre ~ingle-necked flask were connected to an oil pump via a vacuum regulator and cold trap. Under a vacuum of 0.6 mm Hg, disintegration of the gel started within 5 minutes when the flask was heated to a gel temperature of 30 to 40C by means of a thermostat bath, and had ended after a short time.
f) Breakdown of the gel by addition of a cationic surfactant 100 g of the gel prepared according to Example la were initially introduced into a 500 ml conical flask, and 600 ppm of a commercially available surfactant based on coconut-fatty amine were added. Disintegration of the gel took place spontaneously when the components were mixed thoroughly by imple mechanical agitation. A system of two highly fluid phases immiscible with one another resulted.
g) Breakdown of the gel by addition of a polymer having cationic groups 100 g of the gel prepared according to Example la were initially introduced into a 500 ml conical flask, and 4000 ppm of poly-diallyl-dimethyl-ammonium chloride were added. Disintegra-tion of the gel took place spontaneously when the components were mixed thoroughly by simple mechanical agitation. A system of two 2~7~
highly fluid phases Lmmiscible with one another resul~ed.
ample 2 A hydrocarbon-rich gel of 1.6 g of sodium dodecyl-sulphate, 6.4 g of H2O and 392 g of kerosene was prepared as described in Example la, the components being mixed thoroughly with the aid of a Vortex Genie mixer.
Pumping experiments analogous to Example lb gave the following results:
Speed level Duration of experiment Amount of gel pumped 105 minutes 64.9 g 105 minutes 60.2 g 105 minutes 64.3 g The gel was broXen down analogously to Examples ld to lg.
Exam~le 3 A hydrocarbon-rich gel of 1.6 g of a commercially avail-able non-ionic surfactant based on a nonylphenol polyglycol ether, 6.4 g of H2O and 392 g of kerosene was prepared as des-cribed in Example la.
Pumping experiments analogous to Example lb gave the following results:
Speed level Duration of experiment Amount of gel pumped lO5 minutes 55 4 g 105 minutes 58.5 g 105 minutes 54.4 g The gel was broken down analogou~ly to Examples ld and le.
Exam~le 4 A hydrocarbon-rich gel of 1.6 g of sodi~m dodecyl-sulphate, 6.4 g of HzO and 392 g of hexane was prepared as des-cribed in Example la.
Pumping experiments analogous to Example lb gave thefollowing result~:
Speed le~el Duration of experiment Amount of gel pumped 105 minutes 21.4 g lO5 minutes 22.2 g 105 minutes 21.5 g The gel was broken dow~ analogously to Examples ld to lg.
Exam~le 5 A hydrocarbon-rich gel of 1.6 g of a commercially ~3777~!~
available cationic surfactant based on a quaternary ammonium c ~ound, 6.4 g of H20 and 392 g of kerosene was prepared as des-cribed in Example la.
Pumping experiments analogous to Example lb gave the following result~:
Speed level Duration of experiment Amount of gel pumped 5 minutes 283.0 g 5 minutes 288.8 g 5 minutes 248.8 g The gel was broken down analogously to Examples ld to lg, but a crosslinked, partly neutralised polyacrylic acid w~s used in the case of lg.
As described in Examples l to 5, hydrocarbon-rich gels of the following Example~ 6 to l9 were prepared from ligroin, anionic surfactant and water and in each case 41 g of these were broken down with the stated amount of cationic surfactant. The following cationic ~urfactant~ were u~ed:
A 13 35 ~ N NH NH NH NH2 o C1a 35 ~ r NH NH ~ isoc~aHl5 O O
R r-~ r~~ A ~ R
C I N NH NH NH
~ ~ R = polybutenyl molecular weight: 4653.3 Il .
R~y~~~ ~--~ ~_~ ~_~ ~_~
O ~ N NH NH NH NH2 R = polybutenyl molecular weight: 2421.3 ~77~
t_ O l O O O O O O O O O O O O
C I O O O O O O O O O O O O
l O O O O
D :~ ~D ~ D
~ ~ ~ a~ ~ a~/' C`~
~ I
.~,~ I ~ ~ ~ U~ o ~ o ~ I
dP
U I ~ o O O _I _I " ~ ~ ~
o s~ I
~n ~ l I
,~
~D ~ ZG~ ,~ 0 .
~ a 0.,~
u 5 ~ Z~ i1 _I I
.
2~7~
I
O
I cr~ ~
n Ln I oal I.aa,~
C I ~ S: r~,y I
I ~ ~ r~
~n I ,~ 0 0~0 1 t) I r~ I ~ r~
r~
8 1 ~
0 I O ~ 0--~
I
~, I
~ ~ I ~
dP ~ I
~ 0 1 .~ ~, ~a I
Q
o o.,~, ~, o I .
'~ I cocn ,~ tn I cn cn a~-,l I
~ ~ I
I ~U
r~ "
I r~ C~
P
t~ I
r~, r~ I p~
'~-1 I r~ ~a ,~
I _I r~ ~
~o 1 0 o ~a 0 I r~l ~ I Z
~ I t) 0 r~l ~' ,~ I '~ ~ O
o , ~ o O
O ~
O ~ 0 U
_1 1 I
I co cn ~d I _I ~1 2~777~
As described in Examples 1 to 5, hydrocarbon-rich gels of .e following Examples 20 to 36 were prepared from ligroin, cationic surfactant and water and in each case 1 g of these was broken down with the stated amount of anionic surfactant.
_ 15 -' :
2~777~
O I ~
I o ,~ ~o D ~ ~ ~ ~
I ~ ~ o ~ a) 0 '' o $ ~ ~o ~ o o ~ o ~ z U ~ ~ Iu C~ u ~ O
a~o ~ a~S a.~ a~
U z ~_1 Z ~ U ~ u æ u z U Z S,, N ~ O O N N
Ref. 3481 D~.My/asO075 Process for the storaae and transportation of liquid hydrocarbons The present invention relates to the use of hydrocarbon-rich gels as a safe storage and transportation form for liquidhydrocarbons and to a process for the safe storage and the safe transportation of liquid hydrocarbons, the hydrocarbon being converted into a hydrocarbon-rich gel which is broken down again after storage or transportation.
The storage and transportion of liquid hydrocarbons, for example fuels, via roads, rail and on the waterways present a considerable potential hazard. Thus, for example, the high flamm-ability and explosiveness in mixtures of air has led in the past to serious accidents which have caused considerable damage.
Serious ecological damage moreover constantly results from fuels discharged from leaking storage or transportation tanks.
The ob~ect of the present invention is therefore to provide a process for the safe storage and the safe transporta-tion of hydrocarbons.
This ob~ect is achieved, surprisingly, by storing and transporting the hydrocarbons in the form of hydrocarbon-rich gel~.
A hydrocarbon-rich gel is under~tood as meaning a system which consist~ of polyhedrons which are formed from surfactant and are filled with hydrocarbon, water forming a continuous phase in the narrow interstices between the polyhedron~. Systems of this type are known and are described in Angew. Chem. 100 933 (1988) and Ber. Bun~enge~. Phys. Chem. 92 1158 (1988).
Hydrocarbon-rich gels are distinguished by the occurrence of a flow limit. This flow limit is reached when the gel no longer withstand~ a stress imposed on it (shear, deformation) and starts to flow. Below the flow limit, the gel ~tructures have the properties of solid~ and obèy Hooke~s law. Above the flow limit, in the ideal case, the sy~tem is equivalent to a Newtonian fluid.
This means that although hydrocarbon-rich gel~ can be pumped in a simple manner, they cannot flow in the state of re~t because of their properties of solids. They therefore cannot be discharged from defective storage or transportation tanks, and danger to the en~ironment is virtually excluded.
2~777~
The present invention thus relates to the use of hydro-~ bon-rich gels as a safe s~orage and transportation form for liquid hydrocarbons.
The present invention furthermore relates to a process for the safe storage and the safe transportation of liquld hydro-carbons, characterised in that a) the hydrocarbon is converted into a hydrocarbon-rich gel by addition of a surfactant and water and b) after storage or transportation has taken place, the hydro-carbon-rich gel is broken down again.
The surfactant and water are preferably added to the hydrocarbon in amounts such that a hydrocarbon-rich gel of 70 to 99.5% by weight of hydrocarbon, 0.01 to 15% by weight of surfac-tant and 0.49 to 15~ by weight of water is formed.
The surfactant and water are particularly preferably added to the hydrocarbon in amounts such that a hydrocarbon-rich gel of 80 to 99.5% by weight of hydrocarbon, 0.01 to 5% by weight of surfactant and 0.49 to 15% by weight of water is formed.
Hydrocarbons which are particularly suitable for the process according to the invention are n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-dodecane, n-tetradecane, n-hexadecane, cyclohexane, cyclooctane, benzene, toluene, kerosene, petrol, lead-free petrol, heating oil, diesel oil and crude oil.
Anionic, cationic, amphoteric or non-ionic surfactants can be employed to form the hydrocarbon-rich gel-q.
Preferred anionic surfactantc are soaps of the formula R-CH2-COOqNa~
wherein R denotes a hydrocarbon radical having 10 to 20 C atoms;
alkanesulphonates of the fo mula CH--S03/3Na R ' wherein R and R' denote al~yl radicals having together 11 to 17 C atom~;
2~777~5 alkylbenzenesulphonates and -sulfates of the formula R / ~3~ ) n--SO3 Na wherein n is O or 1 and R and R~ denote alkyl radicals having together 11 to 13 S C atoms;
olefinesulphonates of the formula R-CH2-CH = CH-CHz-SO3~Na~
wherein R denotes alkyl having 10 to 14 C atoms;
fatty alcohol sulphates of the formula R-CH2-O-SO3~
wherein R denotes alkyl having 11 to 15 C atoms and Y~ denotes Na~ or triethanolamine;
fatty alcohol polyglycol sulphates of the formula R-CH2-O ( C2H40 ) n-SO3eNa wherein n is 2 to 7 and R denotes alkyl having 8 to 15 C atoms;
sulphosuccinates of the formula 2 ( C2H4O ) n--C--ICH--CH COO Nd0 wherein n is 2 to 6 and R denote~ alkyl having 11 to 13 C atoms;
fatty alcohol polyglycol phosphates of the formula R-CH2-O(C2H4o)npo3HqNa wherein n i~ 2 to 6 and R denotes alkyl having 15 to 17 C atoms;
alkanephosphonates of the formula R-POaH~Na~
wherein R denotes alkyl having 12 to 16 C a~oms;
and ~odium salt~ of oleic acid derivatives, such as oleic acid sarcoside, oleic acid iso~hionate or oleic acid methyl-tauride.
2~7~7t~
Preferred cationic surfactants are aternary ammonium compounds of the formula R R~
N X
R~/ \R4 wherein R~ denotes alkyl having 10 to 22 C atoms, R2 denotes alkyl having 1 to 12 C atoms or benzyl, R3 and R4 independently of one another denote hydrogen or methyl and xe denotes Cle, Bre or CH3So49;
fatty amines, such as, for example, coconut-fatty amines, lauryl-fatty amine, oleyl-fatty amine, stearyl-fatty amine, tallow-fatty amine, dimethyl-fatty amines or primary alkylamines having pure chains of 8 to 22 C atoms;
ammonium borate betaine based on didecylamine;
stearyl-N-acylamido-N-methyl-imidazolinium chlorides of the formula ~C 1 7 H 3 S
H3C CH2CH2NHcl~cl7 35 cle and alkenyl~uccinic acid derivatives of the formulae Il - or o o 2 0GN N H N H N H N~R
wherein R in each case denotes i~o-C1~H3~ or polybutenyl.
Preferred amphoteric surfactants are, for example?~ 777 a. ~lbetaines of the formula wherein R denotes alkyl having 12 to 14 C atoms;
N-carboxyethyl-N-alkylamido-ethylglycinates of the formula R-l-NH-CH2-CH2- I H-CH?-COO
CH 7 - CH zOH
wherein R denotes alkyl having 11 to 13 C atoms; and N alkylamido-propyl-N-dimethylamine oxides of the formula R-C-NH-~CH2) -~
wherein R denotes alkyl having 11 to 13 C atoms.
Preferred non-ionic surfactants are, for example, 1,4-~orbitan fatty acid esters of the formula Hl_OH
H C~
HCOH
CH2 ~nc - R
wherein R denotes alkyl having 11 to 17 C atoms;
fatty alcohol polyglycol ethers of the formula R-O(CH2~CH2~o)nH
wherein n i~ 3 to 15 and R denotes straight-chain or branched alkyl having 9 to 19 C atom~; and . . .
alkylphenol polyglycol ethers of the formula 2 ~ 7 7 7 H- C ~ ~(CH2-CH2~~)n R' wherein n is 3 to 15 and R and R~ denote alkyl having together 7 to 11 C atoms.
S After storage or transportation has taken place, the lLquid hydrocarbon must be recovered again, that is to say the gel structure must be broken down.
This is preferably effected by treatment with mechanical waves, by application of a reduced pressure or vacuum or, if the hydrocarbon-rich gel is formed with the aid of an ionic surfac-tant, by addition of an oppositely charged substance.
Mechanical waves are understood as meaning, in particu-lar, high-frequency pressure waves, that is to say, for example, ultra~ound. When the gel tructure is broken down by ultrasound, the hydrocarbon phase already starts to emerge from the gel structure after only a few seconds. The separation has ended when two highly fluid phases are present side by side. This is as a N le the case after about 30 seconds.
If the gel structure is broken down by application of a reduced pressure or vacuum, the preferred range depends of course on the boiling point of the hydrocarbon. A vacuum of up to 0.1 torr is u~ually advantageous.
Oppositely charged surfactants or polymers or copolymers are preferably employed for breaking down gel structures formed with ionic surfactants.
In the ca~e where gel structures based on cationic sur-factants are broken down, the abovementioned anionic surfactants are particularly preferably employed.
Particularly preferred polymers having anionic groups are, for example, polyacrylates consisting of base elements of the formula --CH;?--~;H--COnH
which can also be crosslinked and/or completely or partly neutralised; ~7~7~5 poly-2-acylamido-2-methyl-propanesu~phonic acids consisting of base elements of the formula --C H ~--f H--C(~NH--C ( CH3 ) 2 C~2 ~i 3 S which can also be crosslinked and/or completely or partly neutra-lised;
or poly-vinylphosphonic acids consisting of base elements of the formula 2 f H
which can also be crosslinked and/or completely or partly neutra-lised.
Mixtures of the polymers mentioned or polymer~ which contain several of the base elements mentioned are also pre-ferred. Polymers which consist, for example, of the above-mentioned base elements having a negative charge and those havinga positive charge can also be employed.
Crosslinked, partly neutralised polyacrylic acid is especially preferred. This moreover has the advantage that, because of its enormous absorption jcapacity for water, it can bind quantitatively the aqueous phase of the gel to be broken down. Because of this absorption capacity for water, crosslinked, partly neutralised polyacrylic acid can break down not only gel structures based on cationic surfactants, but also those based on anionic, amphoteric or non-ionic surfactants.
2~ The abovementioned cationic surfactants are particularly preferably employed in the case of breaking down gel structures based on anionic surfactants.
Particularly preferred polymers having cationic groups are, for example poly-diallyl-dimethyl-ammonium chloride, which can also be cross-linked and/or completely or partly neutralised, or poly-methacrylic acid 2-dimethylaminoethyl ester, consisting of base elements of the formula ' 2 ~ 7 ~ 7 ~ ;~
--CH2~f ~ CH3 )-- CH~, which can also be crosslinked and/or completely or partly neutra-lised.
Mixtures of the polymers mentioned or polymers which contain both the base elements mentioned are also preferred.
Polyme~s which consist, for example, of the abovementioned base elements having a positive charge and those having a negative charge can also be employed.
The breaking down of the gel structure is carried out in a ~imple manner by adding the surfactant or polymer, as such or dissolved in a suitable solvent, to the gel structure and shaking the mixture briefly. The disintegration of the gel then starts ~pontaneously and is faster, the higher the counterion concentra-tion. Appropriate gel disintegration rates are in fact achieved, depending on the ~ystem, if 0.2 to ~5 g, preferably 0.4 to 5 g, of oppo~itely charged surfactant or polymer are added per g of surfactant contained in the gel.
Suitable solvents in which the surfactant or polymer employed for breakdown of the gel can be dissolved are, for example, xylene, water or alcohols.
The concentrations of the surfactants in the solvent~ are not critical, but are preferably from 30% by weight up to satura-tion of the solution. If the hydrocarbon to be stored or trans-ported is a fuel or lubricating oil, it is particularly advan-tageous if surfactants which can remain in the hydrocarbon as an additive are cho3en both for the gel formation and for the break-down of the gel.
For ex~mple, sulphonate~ are known as detergent additives and alkenylsuccinic acid imidoamines are known as dispersant additives (J. Raddatz, W.S. Bartz, 5. Int. Koll. 14. - 16.1.1986, Technische Akademie Esslingen ~dditive f~r Schmierstoffe und Arbeitsflussigkeiten tAdditives for lubricants and working fluids]'). Succinimides are also known as oil and fuel additives (see, for example, EP 198 690, US 4,614,603, EP 119 675, DE 3 814 601 or EP 295 789).
2~777~
EYample 1 a, Preparation 1 g of sodium dodecyl-sulphate was dissolved in 9 g of water and the solution was initially introduced into a wide-necked conical flask. 400 g of ligroin were added at roomtemperature, while stirring vigorously by means of a magnetic stirrer. A hydrocarbon-rich gel system was formed by this proce-dure.
b) Pumping experiments Pumping experiments were carried out with this gel system with the aid of an Ika tube pump. The diameter of the poly-ethylene tube used was 4 mm. The pumpability was recorded as the amount of gel pumped from vessel A to ves~el B after a defined unit of time. The mea3urement results from a duration of the experiment of 5 minutes at different pumping speeds are summar-ised below:
Speed level Duration of experiment Amount of gel pumped 5 minutes 3.8 g 5 minutes 3.7 g 5 minutes 4.4 g 5 minutes 4.1 g 5 minutes 2.9 g 5 minutes 3.8 g 5 minutes 3.9 g 5 minute~ 3.8 g 5 minute~ 4.4 g 5 minutes 4.3 g 5 minutes 4.3 g 5 minutes 4.5 g 5 minutes 4.2 g 5 minutes 4.5 g 5 minutes 3.8 g SummaJ~i~ing, it can be ~aid that, becauqe of the visco-elasticity of the gel ~ystems, the pump delivery proves to be independent of the pumping ~peed.
c) Storage and transportion 2 ~;3 7 r~ 7 ~ ~;
No changes in the consistency or rheological properties oi he gel system were to be found over an observation period of six months. A permanent shear or a violent shaking movement during transportation by rail and road has no influence on the stability of the gel.
d) Breakdown of the gel by ultrasound ln a series of experiments, 50 g of gel each time having the composition described under la were broken down using the Sonifier Cell Disruptor B-30 ultrasollnd unit, different energy 10 levels being set. The time of complete breakdown of the structure was recorded:
Energy level TLme to breakdown Level 10 1 second Level 8 10 seconds 15Level 6 35 seconds Level 4 197 seconds Level 3 390 seconds e) Breakdown of the gel by application of a vacuum 50 g of the gel prepared according to Example la in a 1 litre ~ingle-necked flask were connected to an oil pump via a vacuum regulator and cold trap. Under a vacuum of 0.6 mm Hg, disintegration of the gel started within 5 minutes when the flask was heated to a gel temperature of 30 to 40C by means of a thermostat bath, and had ended after a short time.
f) Breakdown of the gel by addition of a cationic surfactant 100 g of the gel prepared according to Example la were initially introduced into a 500 ml conical flask, and 600 ppm of a commercially available surfactant based on coconut-fatty amine were added. Disintegration of the gel took place spontaneously when the components were mixed thoroughly by imple mechanical agitation. A system of two highly fluid phases immiscible with one another resulted.
g) Breakdown of the gel by addition of a polymer having cationic groups 100 g of the gel prepared according to Example la were initially introduced into a 500 ml conical flask, and 4000 ppm of poly-diallyl-dimethyl-ammonium chloride were added. Disintegra-tion of the gel took place spontaneously when the components were mixed thoroughly by simple mechanical agitation. A system of two 2~7~
highly fluid phases Lmmiscible with one another resul~ed.
ample 2 A hydrocarbon-rich gel of 1.6 g of sodium dodecyl-sulphate, 6.4 g of H2O and 392 g of kerosene was prepared as described in Example la, the components being mixed thoroughly with the aid of a Vortex Genie mixer.
Pumping experiments analogous to Example lb gave the following results:
Speed level Duration of experiment Amount of gel pumped 105 minutes 64.9 g 105 minutes 60.2 g 105 minutes 64.3 g The gel was broXen down analogously to Examples ld to lg.
Exam~le 3 A hydrocarbon-rich gel of 1.6 g of a commercially avail-able non-ionic surfactant based on a nonylphenol polyglycol ether, 6.4 g of H2O and 392 g of kerosene was prepared as des-cribed in Example la.
Pumping experiments analogous to Example lb gave the following results:
Speed level Duration of experiment Amount of gel pumped lO5 minutes 55 4 g 105 minutes 58.5 g 105 minutes 54.4 g The gel was broken down analogou~ly to Examples ld and le.
Exam~le 4 A hydrocarbon-rich gel of 1.6 g of sodi~m dodecyl-sulphate, 6.4 g of HzO and 392 g of hexane was prepared as des-cribed in Example la.
Pumping experiments analogous to Example lb gave thefollowing result~:
Speed le~el Duration of experiment Amount of gel pumped 105 minutes 21.4 g lO5 minutes 22.2 g 105 minutes 21.5 g The gel was broken dow~ analogously to Examples ld to lg.
Exam~le 5 A hydrocarbon-rich gel of 1.6 g of a commercially ~3777~!~
available cationic surfactant based on a quaternary ammonium c ~ound, 6.4 g of H20 and 392 g of kerosene was prepared as des-cribed in Example la.
Pumping experiments analogous to Example lb gave the following result~:
Speed level Duration of experiment Amount of gel pumped 5 minutes 283.0 g 5 minutes 288.8 g 5 minutes 248.8 g The gel was broken down analogously to Examples ld to lg, but a crosslinked, partly neutralised polyacrylic acid w~s used in the case of lg.
As described in Examples l to 5, hydrocarbon-rich gels of the following Example~ 6 to l9 were prepared from ligroin, anionic surfactant and water and in each case 41 g of these were broken down with the stated amount of cationic surfactant. The following cationic ~urfactant~ were u~ed:
A 13 35 ~ N NH NH NH NH2 o C1a 35 ~ r NH NH ~ isoc~aHl5 O O
R r-~ r~~ A ~ R
C I N NH NH NH
~ ~ R = polybutenyl molecular weight: 4653.3 Il .
R~y~~~ ~--~ ~_~ ~_~ ~_~
O ~ N NH NH NH NH2 R = polybutenyl molecular weight: 2421.3 ~77~
t_ O l O O O O O O O O O O O O
C I O O O O O O O O O O O O
l O O O O
D :~ ~D ~ D
~ ~ ~ a~ ~ a~/' C`~
~ I
.~,~ I ~ ~ ~ U~ o ~ o ~ I
dP
U I ~ o O O _I _I " ~ ~ ~
o s~ I
~n ~ l I
,~
~D ~ ZG~ ,~ 0 .
~ a 0.,~
u 5 ~ Z~ i1 _I I
.
2~7~
I
O
I cr~ ~
n Ln I oal I.aa,~
C I ~ S: r~,y I
I ~ ~ r~
~n I ,~ 0 0~0 1 t) I r~ I ~ r~
r~
8 1 ~
0 I O ~ 0--~
I
~, I
~ ~ I ~
dP ~ I
~ 0 1 .~ ~, ~a I
Q
o o.,~, ~, o I .
'~ I cocn ,~ tn I cn cn a~-,l I
~ ~ I
I ~U
r~ "
I r~ C~
P
t~ I
r~, r~ I p~
'~-1 I r~ ~a ,~
I _I r~ ~
~o 1 0 o ~a 0 I r~l ~ I Z
~ I t) 0 r~l ~' ,~ I '~ ~ O
o , ~ o O
O ~
O ~ 0 U
_1 1 I
I co cn ~d I _I ~1 2~777~
As described in Examples 1 to 5, hydrocarbon-rich gels of .e following Examples 20 to 36 were prepared from ligroin, cationic surfactant and water and in each case 1 g of these was broken down with the stated amount of anionic surfactant.
_ 15 -' :
2~777~
O I ~
I o ,~ ~o D ~ ~ ~ ~
I ~ ~ o ~ a) 0 '' o $ ~ ~o ~ o o ~ o ~ z U ~ ~ Iu C~ u ~ O
a~o ~ a~S a.~ a~
U z ~_1 Z ~ U ~ u æ u z U Z S,, N ~ O O N N
3 J~ I
dP ~ I ~ o o 8, t a:~ ~ ~ ~ ~J ~l N N ul ~r u o l ~
li-~ c ~ c =
U ~ ~ U ~ J U
o _I N ~ -- 16 _ N t~ CD N
,:
., , . , - . . ..
2~77~
E
E E E E E E er E E ' E E E~ E
ll I
O
P.
~ I
~ I
d ~ l ~a I
I
U I
I
~ I
O ~ l ~ 1 I e _ u~, -- o ~ C r~ e u e -- a ~c .,~ I c c c o o e e c c c e e e o O I e o e e o e e e o o e o o e I .r ~c e ~
U ~ C ~~ ~ ~ e ,1 1 ~c e e ~o G r~ G 1~-1G 1-- e ~c G ~. 01 G Cl 0~ G G Cl`0~ 01 ~ G
~ I
a~
,U ,, ~ ~ ~ ~ ~ - ~ ~ s Z cZ ~Z a;Z --~q s U s ~r C q~ o c~ v o c c c u u~ U ~e:~G ~Z ~ ~
I`~ N ~ ~1 S ~1 S S S S S~G S
~ _ _ ~ ~ e U ~
U `U . ~ U -- U
I
cn .
~ I .
_I I
~ e ~ C -- ~ ~ C
As described in Examples 1 to 5, hydrocar~on~ f ~e following Examples 37 to 50 were prepared from ligroin, surfactant and water and in each case 1 g of these was broken down wi.th the stated amount of an oppositely charged polymer.
The following polymers were employed:
Polymer l: polyacrylate Polymer 2: poly-dialkyl-dimethyl-ammonium chloride Polymer 3: poly-2-acrylamido-2-methyl-propanesulphonic acid Polymer 4: poly-vinylphosphonic acid Polymer 5: poly-methacrylic acid 2-dimethylamino-ethyl ester . : ..: , '' ' ' ' ' ~'"""' ' ''' ' ~' .: .
' :' ' ' : ' :
~7~7~
O I _~ CD ~ U~t` ~ Ul q , , .~ , C
~ ~0 ~ ,a c W
3 , or @u ~n u ~ o u ~
S ~ U~
' u oz~ u æu~ u ~ z ~ ' I
I
3 ~ I o~ o u~ u~ o u) ~
aJ I -~J I
dP C I
~1 U I ~ ~ o o ,~
a~ I . . . . .
~4~ 1 o o o o O O o O h I
,1 ~ I
~ U~ I
rl I
~a I
Q
O O I co c~ ~ ~ co ~ ~r U ~ I . . . .
I
.
, ~ ~
o~
--~ --I o .
, a ~ 3 ~ 0 ~ , u c u~ u, ~ u, u ~
,~ ~ ~o ~ o ' ~o ~o _l ~o ~~ co ~ o o c~ I u ~ u ou ~a ~ u u ' _I I
I O ~I N ~
x I _ 19 -
dP ~ I ~ o o 8, t a:~ ~ ~ ~ ~J ~l N N ul ~r u o l ~
li-~ c ~ c =
U ~ ~ U ~ J U
o _I N ~ -- 16 _ N t~ CD N
,:
., , . , - . . ..
2~77~
E
E E E E E E er E E ' E E E~ E
ll I
O
P.
~ I
~ I
d ~ l ~a I
I
U I
I
~ I
O ~ l ~ 1 I e _ u~, -- o ~ C r~ e u e -- a ~c .,~ I c c c o o e e c c c e e e o O I e o e e o e e e o o e o o e I .r ~c e ~
U ~ C ~~ ~ ~ e ,1 1 ~c e e ~o G r~ G 1~-1G 1-- e ~c G ~. 01 G Cl 0~ G G Cl`0~ 01 ~ G
~ I
a~
,U ,, ~ ~ ~ ~ ~ - ~ ~ s Z cZ ~Z a;Z --~q s U s ~r C q~ o c~ v o c c c u u~ U ~e:~G ~Z ~ ~
I`~ N ~ ~1 S ~1 S S S S S~G S
~ _ _ ~ ~ e U ~
U `U . ~ U -- U
I
cn .
~ I .
_I I
~ e ~ C -- ~ ~ C
As described in Examples 1 to 5, hydrocar~on~ f ~e following Examples 37 to 50 were prepared from ligroin, surfactant and water and in each case 1 g of these was broken down wi.th the stated amount of an oppositely charged polymer.
The following polymers were employed:
Polymer l: polyacrylate Polymer 2: poly-dialkyl-dimethyl-ammonium chloride Polymer 3: poly-2-acrylamido-2-methyl-propanesulphonic acid Polymer 4: poly-vinylphosphonic acid Polymer 5: poly-methacrylic acid 2-dimethylamino-ethyl ester . : ..: , '' ' ' ' ' ~'"""' ' ''' ' ~' .: .
' :' ' ' : ' :
~7~7~
O I _~ CD ~ U~t` ~ Ul q , , .~ , C
~ ~0 ~ ,a c W
3 , or @u ~n u ~ o u ~
S ~ U~
' u oz~ u æu~ u ~ z ~ ' I
I
3 ~ I o~ o u~ u~ o u) ~
aJ I -~J I
dP C I
~1 U I ~ ~ o o ,~
a~ I . . . . .
~4~ 1 o o o o O O o O h I
,1 ~ I
~ U~ I
rl I
~a I
Q
O O I co c~ ~ ~ co ~ ~r U ~ I . . . .
I
.
, ~ ~
o~
--~ --I o .
, a ~ 3 ~ 0 ~ , u c u~ u, ~ u, u ~
,~ ~ ~o ~ o ' ~o ~o _l ~o ~~ co ~ o o c~ I u ~ u ou ~a ~ u u ' _I I
I O ~I N ~
x I _ 19 -
Claims (8)
1. Use of hydrocarbon-rich gels as a safe storage and transportation form for liquid hydrocarbons.
2. Process for the safe storage and the safe transportation of liquid hydrocarbons, which process comprises a) converting the hydrocarbon into a hydrocarbon-rich gel by addition of a surfactant and water, b) storing or transporting the hydrocarbon-rich gel, and c) breaking down the hydrocarbon-rich gel after storage or transportation has taken place.
3. Process according to claim 2, wherein the surfactant and water are added to the hydrocarbon in amounts such that a hydrocarbon-rich gel of 70 to 99.5% by weight of hydrocarbon, 0.01 to 15% by weight of surfactant and 0.49 to 15% by weight of water is formed.
4. Process according to claim 3, wherein the surfactant and water are added to the hydrocarbon in amounts such that a hydrocarbon-rich gel of 80 to 99.5% by weight of hydrocarbon, 0.01 to 5% by weight of surfactant and 0.49 to 15% by weight of water is formed.
5. Process according to claim 2, 3 or 4, wherein n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-dodecane, n-tetradecane, n-hexadecane, cyclohexane, cyclooctane, benzene, toluene, kerosene, petrol, lead-free petrol, heating oil, diesel oil or crude oil are employed as the hydrocarbons.
6. Process according to claim 2, 3 or 4, wherein anionic, cationic, amphoteric or non-ionic surfactants are employed as the surfactant.
7. Process according to claim 2, 3 or 4, wherein after storage or transportation has taken place, the hydrocarbon-rich gel is broken down by treatment with mechanical waves, applica-tion of a reduced pressure or vacuum or, if the hydrocarbon-rich gel is formed with the aid of an ionic surfactant, by addition of an oppositely charged substance.
8. Process according to claim 7, wherein a hydrocarbon-rich gel formed with the aid of ionic surfactants is broken down by oppositely charged surfactants or polymers or copolymers.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4129943A DE4129943A1 (en) | 1991-09-09 | 1991-09-09 | PROCESS FOR STORAGE BZW. FOR THE TRANSPORT OF LIQUID HYDROCARBONS |
| DEP4129943.4 | 1991-09-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2077705A1 true CA2077705A1 (en) | 1993-03-10 |
Family
ID=6440200
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2077705 Abandoned CA2077705A1 (en) | 1991-09-09 | 1992-09-08 | Process for the storage and transportation of liquid hydrocarbons |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5276248A (en) |
| EP (1) | EP0531807B1 (en) |
| JP (1) | JPH07179870A (en) |
| AT (1) | ATE119934T1 (en) |
| CA (1) | CA2077705A1 (en) |
| DE (2) | DE4129943A1 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996033374A1 (en) * | 1995-04-18 | 1996-10-24 | Nikolai Ivanovich Selivanov | Method of heating a liquid and a device therefor |
| EP0826416A4 (en) * | 1995-04-18 | 1998-06-10 | Nikolai Ivanovich Selivanov | Method of conditioning hydrocarbon liquids and an apparatus for carrying out the method |
| US6194622B1 (en) * | 1998-06-10 | 2001-02-27 | Exxonmobil Upstream Research Company | Method for inhibiting hydrate formation |
| US6222083B1 (en) | 1999-10-01 | 2001-04-24 | Exxonmobil Upstream Research Company | Method for inhibiting hydrate formation |
| US6994104B2 (en) * | 2000-09-05 | 2006-02-07 | Enersea Transport, Llc | Modular system for storing gas cylinders |
| US6584781B2 (en) | 2000-09-05 | 2003-07-01 | Enersea Transport, Llc | Methods and apparatus for compressed gas |
| US7405188B2 (en) | 2001-12-12 | 2008-07-29 | Wsp Chemicals & Technology, Llc | Polymeric gel system and compositions for treating keratin substrates containing same |
| US7183239B2 (en) * | 2001-12-12 | 2007-02-27 | Clearwater International, Llc | Gel plugs and pigs for pipeline use |
| US8273693B2 (en) * | 2001-12-12 | 2012-09-25 | Clearwater International Llc | Polymeric gel system and methods for making and using same in hydrocarbon recovery |
| US8065905B2 (en) | 2007-06-22 | 2011-11-29 | Clearwater International, Llc | Composition and method for pipeline conditioning and freezing point suppression |
| US8099997B2 (en) | 2007-06-22 | 2012-01-24 | Weatherford/Lamb, Inc. | Potassium formate gel designed for the prevention of water ingress and dewatering of pipelines or flowlines |
| US20130025857A1 (en) * | 2011-07-27 | 2013-01-31 | Conlen Surfactant Technology, Inc. | Preserving oil gravity |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2890257A (en) * | 1955-12-28 | 1959-06-09 | Pure Oil Co | Method of stabilizing odorless naphthas during storage |
| US3378418A (en) * | 1966-04-11 | 1968-04-16 | Petrolite Corp | Method of resolving thixotropic jet and rocket fuel emulsions |
| US3416320A (en) * | 1967-07-14 | 1968-12-17 | Exxon Research Engineering Co | Turbo-jet propulsion method using emulsified fuels and demulsification |
-
1991
- 1991-09-09 DE DE4129943A patent/DE4129943A1/en not_active Withdrawn
-
1992
- 1992-08-27 AT AT92114585T patent/ATE119934T1/en not_active IP Right Cessation
- 1992-08-27 EP EP19920114585 patent/EP0531807B1/en not_active Expired - Lifetime
- 1992-08-27 DE DE59201653T patent/DE59201653D1/en not_active Expired - Fee Related
- 1992-09-02 US US07/938,996 patent/US5276248A/en not_active Expired - Fee Related
- 1992-09-08 JP JP23984492A patent/JPH07179870A/en not_active Withdrawn
- 1992-09-08 CA CA 2077705 patent/CA2077705A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| EP0531807A1 (en) | 1993-03-17 |
| US5276248A (en) | 1994-01-04 |
| DE59201653D1 (en) | 1995-04-20 |
| EP0531807B1 (en) | 1995-03-15 |
| JPH07179870A (en) | 1995-07-18 |
| ATE119934T1 (en) | 1995-04-15 |
| DE4129943A1 (en) | 1993-03-11 |
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