CN87106648A - Blended overbase complex antifouland compositions and application thereof - Google Patents
Blended overbase complex antifouland compositions and application thereof Download PDFInfo
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- CN87106648A CN87106648A CN198787106648A CN87106648A CN87106648A CN 87106648 A CN87106648 A CN 87106648A CN 198787106648 A CN198787106648 A CN 198787106648A CN 87106648 A CN87106648 A CN 87106648A CN 87106648 A CN87106648 A CN 87106648A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F15/00—Other methods of preventing corrosion or incrustation
- C23F15/005—Inhibiting incrustation
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G9/14—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means
- C10G9/16—Preventing or removing incrustation
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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Abstract
By adding the scale inhibitor of a certain amount of effective inhibition fouling, suppress oil, the fouling in gas and the petroleum chemistry complete processing.This scale inhibitor contains the high alkaline complex of magnesium oxide, magnesiumcarbonate, fatty acid magnesium salt and sulfonic acid magnesium salts.
Description
Be included in all technology in the processing of oil, gas and petroleum chemistry, for example reform, technologies such as hydroforming, absorption, hydrocracking, isomerization, extracting, cracking, fractionation, hydrofining, desalination, all need to make hydrocarbon material flow to bear quite high temperature.The raising of temperature, process furnace commonly used and interchanger are realized, make hydrocarbon feed, product and intermediate product closely contact with warmed-up surface like this.As you know, these operational conditions have been encouraged the formation of scale deposition thing, thereby have greatly limited refining ability and flow velocity.
Many positions in the refining process are easily fouling all, comprises preheating heat exchanger, hydrodesulfurization unit and fluidized catalytic cracker, overhead condenser, reformation reboiler, coking heater, vacuum distillation tower, the alkylation reboiler of crude battery for example etc.
Scale problems not only is especially severe in petroleum refining industry, and divide in the purification operations of gold-plating device at gas, with all technology of petroleum chemistry for example in the production of ethene, vinylbenzene, divinyl, isoprene, vinyl cyanide and other chemical, scale problems also is a problem that is difficult to solve always.
The hydrocarbon or derivatives thereof when being exposed to the retardance face of metal in the processing unit or other material, can be observed under high temperature at any time, follows the physics of the hydro carbons of thermal initiation and derivative or chemization to become and the scale deposition thing that forms.As everyone knows, these settlings greatly reduce the heat transfer property of affected systems, and be removed be and the difficulty.By incrustation with its increase that removes the operation and maintenance costs that is caused is very considerable.Therefore for eliminating scale problems, people make great efforts to have carried out various trials, have advised several different methods, or prevent that incrustation from forming, or remove incrustation.These methods have all obtained the different effect of degree, but basic problem still exists.
By improving the scale deposition thing that the hydrocarbon raw material physics that technological temperature causes and/or the chemization sell of one's property are given birth to, can form by the material of viscosity, tarry, polymeric or carbon class.Modal scale deposition thing generally can be divided into inorganic salt, corrosion product, organometallics, organic polymer and coke.Inorganic salts may be to enter process system with crude oil as sodium-chlor, calcium chloride and magnesium chloride.Organometallics may be present in the raw material, also may be to form at heat-transfer surface with corrosion product or other metal compound of bringing system in.The formation of organic polymer is normally caused by unsaturated hydro carbons reaction.Deposition of carbon is usually relevant with the appearance of the caused focus of accumulation of scale deposition thing.Therefore can show that in these complete processings, the metal of scale deposition thing and organic element are to interact.
For reducing the accumulation of scale forming matter in the processing unit, some measures have been taked, comprising polishing and coating, to reduce avidity to scale forming matter to processing unit.Yet prevent that with the permanent protection coating metallic surface of coating the scale deposition thing from forming, because coating itself causes the heat-transfer capability loss, so produce the loss of process efficiency inevitably.
Another does not need the investment of processing unit coating, does not cause the measure of heat-transfer capability loss yet, is to add can prevent that foulant from forming or prevent that incrustation from adhering to the chemical preparations of processing unit in hydro carbons.In order to prevent or alleviate the formation of scale deposition thing in the process system, proposed a large amount of relevant compositions, but none is considered to success fully.
The present invention relates to novel antifouland compositions and application thereof, to suppress in oil, gas and the petroleum chemistry processing and the fouling of equipment used in other organic materials hot-work.Specifically, the present invention relates in refinery, gas fractionation plant and petroleum chemistry device, use the dispersed high alkalinity complexing of colloid scale inhibitor.More particularly, the present invention relates to the high alkaline complex of magnesium oxide and magnesiumcarbonate and at least a complexing agent, and they do the application of scale inhibitor in oil, petroleum chemistry and gas process operation.
Far-ranging various scale inhibitor is existing to be adopted, and attempts to suppress the relevant scale formation of decomposition with crude oil and treated oil, gas and petrochemical complex feed stream.A part but the patent of representational relevant antifouland compositions and application thereof is following listed:
2，895，913????4，410，418
3，364，130????4，425，223
3，492，219????4，431，514
3，546，097????4，440，625
3，666，656????4，444，649
3，772，182????4，456，526
4，024，051????4，469，586
4，107，030????4，510，041
4，200，518????4，511，457
4，319，063????4，529，500
4，397，737????4，552，643
4，404，087????4，556，476
These patents have been described: the oil-dispersing property of using in lubricating oil contains magnesium organic composite (2,895,913); The acid amides coacervation prod that in oil processing equipment, uses; The metal passivator that in hot petroleum feeding, uses; The mixture of methacrylate polymer and nitrogenous material; Oil soluble add-on type multipolymer; The mixture of nitrogenous methacrylate polymer; The mixture of Schiff's base and diarylamine; Phosphorated mineral acid and salt; Sulfanilate; Polyalkylene amine; The mixture of sulfonate; The mixture of amine and phenylhydrazine; Poly-(oxyalkylene) carbamate; Metal as tin, antimony and germanium and so on; Halogenous silicon compound; The mixture of phosphorous acid ester and hydrocarbon sulfonate; The reaction product of polyalkylene amine and hydroxy fatty acid; The mixture of azanol and organic surface active agent; Phosphoric acid salt; The mixture of azanol and pyrocatechol; Saturated sulfoxide; The mixture of thiodiphenylamine and phenol; The mixture of thiodiphenylamine, pyrocatechol and Resorcinol; Phenothiazine dimer; The composition of tin, copper and antimony; The mixture of thiodiphenylamine and azanol.In addition, UK Patent Application 2017747A has described the scale inhibitor that two-2-ethylhexyl sodium sulfosuccinate is used as crude oil; English Patent 2021144B describes the poly-alkylene chlorine sulfoxylate of 3 usefulness and prevents and remove the incrustation of hydrocarbon feed logistics on refining equipment.
Contain for example complex compound fluid dispersion liquid or " solution " of the high alkalinity oil-proofness of magnesium and calcium, their preparation method and using method are known to the technician of this professional domain.The product that term " high alkalinity (Overbase) " is meant metal base/acid-respons in history and is generated contains the amount of metal that surpasses the required stoichiometric quantity of the neutral organic acid salt that generates this alkali in this product.Adopted term comprises " alkalescence ", " overbasic " and " hyperalkaline " between often using.
Known have several different methods to prepare overbasic metallic dispersion liquid.The representational United States Patent (USP) that discloses preparation high alkalinity metal complex compound method is following listed:
U.S.2,585,520 disclose the high alkalinity magnesium that can be used as lubricating oil additive and the preparation method of calcium sulfonated petro-leum.
U.S.2,895,913 disclose the stable oil-dispersing property that can be used as lubricating oil additive, the preparation method of high alkalinity organo-magnesium compound.
U.S.3,057,896 discloses the preparation method of the high alkaline azochlorosulfonate acid sodium that can be used as lubricating oil additive.
U.S.3,150,089 disclose the stable dispersions of the high alkalinity organo-magnesium compound that can be used as lubricating oil additive.
U.S.3,629,109 disclose the preparation method of the high alkalinity organic-magnesium complex compound that can be used as lubricant and fuel dope.
U.S.3,764,536 disclose a kind of calcium salt that can be used as the alkenyl succinimide of dispersing additives of lubricants.
In addition, U.S.3,776,835 disclose antiscale washing composition-disperser composition of using as the high temperature, hydrocarbon logistics.These compositions comprise sulfonate, the particularly neutrality of Phenylsulfonic acid and alkaline metal salt, the neutrality of phosphonic acids and phosphonothionic acid and basic salt, the neutrality of phenol and carboxylic acid and basic salt, and carboxylate salt-phenates, alkenyl succinimide, basic metal naphthenate, amine and carboxylic acid.Mentioned the extensive stock scale inhibitor simultaneously, comprised the oxyethyl group pyrocatechol, poly-hydroxyl-oxethyl amine, the composition of metal passivator, phenol amine and succinimide, the composition of the water-soluble salt of morpholine and oxyethyl group tetrahydroglyoxaline.
U.S.3,865,737 disclose the preparation method of the high alkalinity organic-magnesium complex compound dispersion that can be used as lubricating composition additive fluid.
U.S.4,129,589 disclose the preparation method of the sulfonic acid high alkalinity magnesium salts that can be used as slip additive.
U.S.4,163,728 disclose the preparation method of the stable fluid organic-magnesium complex compound dispersion that can be used as the acid neutralization additive of lubricating oil.Disclosed compound is overbasic.
U.S.4,293,429 disclose magnesium carboxylates and magnesium oxide high alkalinity preparation process of mixture that inferior fine particle magnesium oxide fluid disperses formation.This compound can be used as lubricant additive.
U.S.4,295,981 disclose the preparation method of the high alkalinity magnesium phenates that can be used as lubricating oil additive.
U.S.4,298,482 have described the magnesium salts and the magnesium hydroxide high alkalinity preparation process of mixture of nano sized particles dispersion form.This overbased material can be used as the acid neutralizing agent of lubricating oil or oil fuel.
U.S.4,347,147 disclose sulfonate and the magnesian preparation method of the very little magnesium of granularity.
U.S.4,474,710 disclose magnesium hydroxide or the high alkalinity preparation process of mixture of magnesiumcarbonate in liquid sulfonic acid magnesium dispersion agent.This material can be used as lubricant additive.
The above patent none suggestion uses the high alkaline complex of metal to reduce the scale problems relevant with refining process as described herein.
In above-mentioned patent, U.S.3,865,737,4,163,728,4,293,429 and 4,298,482 disclose is to the elaboration of prior art with to prepare the high alkalinity metal complex compound with the dispersion form be useful especially.So this, the disclosure of these patents promptly about the preparation of high alkalinity metal compound and the argumentation of composition, is incorporated herein and does reference.U.S.3 particularly, 865,737 1-9 hurdles, U.S.4,163,728 1-4 hurdles, U.S.4,293,429 1-3 hurdle and U.S.4,298,482 1-4 hurdles.
The present invention relates to novel antifouland compositions, described composition is the mixing high alkaline complex that contains oil-proofness colloid dispersive magnesium oxide and magnesiumcarbonate particulate and complexing agent; The invention still further relates to these complexing antifouland compositions and in refining of petroleum technology, be used for suppressing the using method of fouling, particularly high-temperature scaling (as 500～1200).
As previously mentioned, the antiscale in oil, gas and the petroleum chemistry complete processing is the problem of a special trouble always.The complex nature of the problem not only is the character of scale forming matter, but also is that the different zones of technological operation or device have different environment, different raw materials and different purpose products.The scale problems in a zone of refinery, not necessarily the antiscaling treatment method with different zones is identical, therefore, must decompose oil refining process and come, device ground of a device is handled, and the fouling character of each device must be determined, to carry out suitable processing.
Using the antiscale chemical in the following column region of refinery is particularly important.
1. after the desalination but before entering crude battery, in crude stream, add scale inhibitor, promptly add scale inhibitor in the process-stream after the desalination that enters preheater.
2. in effluent heat exchanger package (long residuum), add scale inhibitor, promptly in the atmospheric tower overhead product of crude battery, add scale inhibitor.
3. flowing to and flowing out logistics and add scale inhibitor to hydrofining and hydrotreater reactor.
4. to atmospheric tower overhead product (oil at the bottom of the tower), comprise to pump around circuit gentle/add scale inhibitor in oil decompression process furnace and the vacuum distillation tower feed stream.
5. in the charging of coking furnace (postpone or fluidisation), coking furnace itself, coupled transfer limes and pump around circuit, add scale inhibitor.
6. in the logistics of reboiler forward direction inflow alkyl plant main fractionating tower, add scale inhibitor, in the reboiler pump around circuit, add scale inhibitor, also should add scale inhibitor to reboiler itself.
7. to the charging of fluidized catalytic cracker preheater, flow into the logistics of slurry oil heat-exchange system, comprise in bottoms, pump around circuit and the catalytic cracking unit pump around circuit of main fractionating tower adding scale inhibitor by cracking unit.
Each zone of above-mentioned refinery not necessarily has identical feature because its particular environment is all operated in the mode that differs from one another with other zone of refinery.
Illustrate the significant points that needs to add scale inhibitor in the refinery below:
The crude unit preheating heat exchanger
Crude unit vacuum residuum interchanger
Crude unit underpressure distillation process furnace and residual oil
The fluidized catalytic cracker preheater
The fluidized catalytic cracker slurry oil recycle system
The fluidized catalytic cracker process furnace
Delay coking device
Fluid coker
Hydrotreater
Hydroeracking unit
Reboiler
The hydrogenating desulfurization device
Heat exchanger
Heat separator
Pump around circuit
The process-stream pipeline
Find according to the present invention, if prepare magnesium oxide and magnesiumcarbonate together with the organic acid complexing agent, that not products therefrom be a kind of high alkaline complex that contains superfine (preferably submicron) magnesium oxide and magnesiumcarbonate and complexing agent metal magnesium salts.Theoretically, in the process of preparation metal oxide or carbonate, the existence of complexing agent is arranged, and it is poly-that knot takes place the fine particle that can prevent metal oxide or carbonate, and make fine particle stably dispersing in the used thinner of reaction and in the later hydrocarbon material flow.
The essence of overbased material is difficult for understanding, and once proposes, and they contain acidic substance and contact formed salt with alkali reaction metallic compound (as the oxyhydroxide of metal).Also proposed in addition, they contain " polysalt ".Can believe that these two kinds of formulations are right, but not exclusively really correct.The overbased material of the present invention's preparation is the high alkaline complex of a kind of metal oxide or carbonated and a kind of organic acid dispersion agent or stablizer (being complexing agent) formation.The character of formed this complex compound is not also understood for people fully.
Therefore, as used in this specification sheets " high alkaline complex " be the complex compound of the magnesium salts of magnesium oxide or magnesiumcarbonate and organic acid " complexing agent ".Based on the normal stoichiometric quantity of special metal alkali and acid, high alkaline complex contain metal above stoichiometric quantity (with respect to the chemical equivalent number of the acid complexing agent of alkaline metal cpds reacting generating complex).For example, the feature of " neutrality " or " just " metal-salt of acid is a metal and the equivalence ratio of acid is 1: 1, and the feature of high alkalinity salt be this than higher, for example 1.1: 1,2: 1,5: 1,10: 1,15: 1,20: 1,30: 1 etc.Term " metal than " is used for the ratio of the equivalents that requires in the equivalent of metal pair acid in expression (a) high alkalinity salt and (b) normal salt, according to the common stoichiometric quantity of one or more metals that participate in and one or more acid.Like this, the metal ratio that contains the high alkalinity magnesium salts oil dispersion of 2 angelic acids and 20 equivalent magnesium is 10 (i.e. 20 ÷ (1+1)).
In this manual, for example magnesium is regarded as each nucleidic mass and had 2 equivalents, magnesium oxide (MgO) and magnesium hydroxide (Mg(OH)
2) every mole have 2 equivalents.Each sour hydrogen of organic acid or acidic group have a normal acid.Like this, monocarboxylic acid or monobasic sulfonic acid or their suitable derivative, as ester, ammonium salt and metal-salt, every equimolar acid, ester or salt have an equivalent; Disulfonic acid, dicarboxylic acid or normal derivative have 2 equivalents for every mole.The alkali reaction metallic compound, as magnesium oxide and magnesiumcarbonate, every mole has 2 equivalents (being 2 equivalents of each atoms metal amount).
Complex compound scale inhibitor of the present invention is the high alkaline complex of the magnesium salts of magnesium oxide and magnesiumcarbonate and organic acid complexing agent.
Mixing high alkaline complex used among the present invention can prepare with the known method for preparing high alkalinity salt of any prior art, as long as formed high alkaline complex is the form that is particulate (preferably being submicron) separately, in oil, forms stable dispersion and get final product.Therefore, the better method of the high alkaline complex of preparation magnesium oxide/complexing agent of the present invention is to form magnesium alkali (as Mg(OH)
2), the mixture of complexing agent (as the lipid acid of ready denier oil acid and so on, its amount calculates the aequum much less than oxyhydroxide reactive chemistry) and a kind of non-volatile thinner.This mixture heating up to temperature is approximately 250～350 ℃, the high alkaline complex that combines by resultant magnesium oxide and complexing agent magnesium salts.Magnesiumcarbonate/complexing agent high alkaline complex just will pass through initial reaction mixture with carbon dioxide with method preparation same as described above.
The above-mentioned method for preparing high alkaline complex of the present invention is at U.S.P4, has specially in 163,728 and states, and this paper quotes the document as reference, for example, and Mg(OH wherein)
2With the carboxylic acid complexing agent mixture, in suitable non-volatile thinner, be heated to about 280～330 ℃ of temperature.
Being used for complexing agent of the present invention is lipid acid, as ready denier oil acid, and sulfonic acid.Itself has oil soluble sulfonic acid, so particularly useful.The oil-soluble derivative that these are sour, their metal-salt for example, ammonium salt and ester (ester that particularly has the rudimentary aliphatic alcohol that reaches six carbon atom is as the ester of low-level chain triacontanol) can be used to replace or with the free acid combined utilization.When mentioning acid, also comprise its suitable derivative, unless can obviously find out want only be acid.
The oil-soluble sulfonic acid that is suitable for is by following general formula:
In formula I, T comprises phenyl ring, cyclic aliphatic or heterocycle, as benzene, naphthalene, anthracene, and 1,2,3,4, the monocycle of-tetraline, thianthrene, cyclopentenes, pyridine or cyclohexyl biphenyl etc. or how ring-like ring.Yet, T ordinary representation aromatic hydrocarbon ring, particularly phenyl ring or naphthalene nucleus.R among the Rx, for instance, can be an aliphatic group, as alkyl, alkenyl, alkoxyl group, alkoxyalkyl, carbonyl alkoxyalkyl, aralkyl group or other hydrocarbon or mainly be the group of hydrocarbon, x is 1 at least, and supplementary condition are that the represented group of Rx can make acid have oil soluble.The represented group of Rx should contain about 8 aliphatic carbon atoms at least in other words, preferably contains about 12 aliphatic carbon atoms at least.In general, x is arbitrary integer of 1-3.The mean value of r and y per molecule is approximately 1 to 4.
R ' in the general formula II is the cyclic aliphatic alkyl of aliphatic group or aliphatic group replacement or is the base of hydrocarbon in essence.When R ' is aliphatic group, should contain about 8 to 20 carbon atoms at least, when R ' was the cyclic aliphatic base of aliphatic group replacement, aliphatic substituting group should contain about 4 to 16 carbon atoms.R " the example cyclic aliphatic base that has alkyl, thiazolinyl and alkoxyalkyl and aliphatic group to replace, wherein aliphatic substituting group is alkoxyl group, alkoxyalkyl, carbonyl alkoxyalkyl etc.In general, the cyclic aliphatic base is a naphthenic hydrocarbon ring or a cycloolefin ring, as pentamethylene, hexanaphthene, tetrahydrobenzene, cyclopentenes like this type of.The particular instance of R ' has the hexadecyl cyclohexyl, dodecyl cyclohexyl, hexadecyl oxyethyl group and vaccenic acid base, and oil, saturated and undersaturated paraffin and polyolefine (comprising that each olefin monomer unit contains the poly-monoene or the polydiene of about 1 to 8 carbon atom) deutero-group.In formula I and the II, T, R and R ' also can contain other substituting group, as hydroxyl, sulfydryl, halogeno-group, nitro, amino, nitroso-group, carbonyl, lower alkoxycarbonyl etc., only otherwise the principal character of destroying hydrocarbon gets final product.
Here the preferred sulfonic acid that uses comprises alkylsulphonic acid, an alkarylsulphonic acid, dialkyl group sulfonic acid, two an alkarylsulphonic acid, aryl sulfonic acid, for example ethylsulfonic acid, Phenylsulfonic acid, Witco 1298 Soft Acid and complicated azochlorosulfonate acid mixture are as mahogany sulfonic acid and mahogany acid.
In addition, have illustrative sulfonic acid example and also have mahogany sulfonic acid; vaseline sulfonic acid; the naphthene sulfonic acid that single wax or many wax replace; the hexadecyl chlorobenzenesulfonic acid; hexadecyl phenol sulfonic acid; curing hexadecyl phenol sulfonic acid; n-Hexadecane oxygen decanoyl Phenylsulfonic acid; dicetyl thianthrene sulfonic acid; the dilauryl beta-naphtholsulfonic acid; two decanoyl nitro naphthylidene sulfonic acid; paraffin sulfonic acid; unsaturated paraffin sulfonic acid; the paraffin sulfonic acid that hydroxyl replaces; four pib sulfonic acids; four amylene sulfonic acid; chloro paraffin sulfonic acid; nitrosyl is for paraffin sulfonic acid; oil cycloalkanes sulfonic acid; hexadecyl cyclopentyl sulfonic acid; lauryl cyclohexyl sulfonic acid; the cyclohexyl sulfonic acid that single wax and many wax replace etc. are like that.
Term used herein " mahogany acid " is intended to comprise processing method according to routine by the well-known class sulfonic acid of petroleum products deutero-, and these methods are at U.S.P.2,480,638,2,483,800,2,717,265,2,726,261,2,794,829,2,832,801,3,225,086,3,337, have disclosed in 613,3,351,655.Sulfonic acid United States Patent (USP) 2,616,904,2 in early days in formula I and the II scope, 616,905,2,723,234,2,723,235,2,723,236,2,777,874 and other United States Patent (USP) of introducing of these patents in argumentation is arranged, therefore visible these oil-soluble sulfonic acid are that the present technique field is known, have no need for further discussion here.
Certainly, above-mentioned organic acid mixture and its derivative also can be used for preparing scale inhibitor of the present invention.
Scale inhibitor of the present invention is the high alkaline complex of the magnesium oxide of (A) a kind of particulate and fatty acid magnesium salt and the mixture of the high alkaline complex of the magnesiumcarbonate of (B) a kind of particulate and sulfonic acid or azochlorosulfonate acid mixture magnesium salts.
According to U.S.4,163,728 methods of being narrated can prepare the high alkaline complex of the magnesium salts of magnesium oxide and ready denier oil acid.
The high alkaline complex of the magnesium salts of magnesiumcarbonate and sulfonic acid can be used similar methods at Mg(OH)
2Introduce CO when reacting with sulfonic acid
2Preparation.
The high alkaline complex of the magnesium salts of magnesiumcarbonate and sulfonic acid also can have been bought on market, and commodity are Witco M400.
More than weight ratio approximately from 0.25 to 10 to 10 to 0.25 between two kinds of high alkaline complex.
Following example explanation blended high alkaline complex is as the application of scale inhibitor.
Embodiment
Australian new fractionation plant processing commingled crude and liquefied petroleum gas (LPG) (LPG) turn round after two months, and pipeline suffers serious fouling and vibration.Cleaning deethanizing column reboiler, and fouling is growing on and on.Stop after six months producing.Clean this device to remove incrustation in reboiler and the deethanizing column.Being blocked in fouling in the deethanizing column has more than four feet thickly, and the diameter of operation pipeline flow surface reduces to 2 inches by 16 inches.The incrustation of from reboiler, removing, the quality difference, the hard coaly material from soft putty to crystal form has.
After the removing,, in the deethanizing column charging, add scale inhibitor of the present invention by the 100ppm that accounts for hydrocarbon stream weight.Scale inhibitor is the high alkaline complex and (B) mixture of the high alkaline complex (Witco M400) of a kind of magnesiumcarbonate and sulfonic acid magnesium salts of the magnesium salts of (A) a kind of magnesium oxide and ready denier oil acid, and both weight ratios are approximately 1: 1.
The fouling inspection is to finish by the total heat transfer pipe of measuring reboiler.Device has gone into operation 15 months now, does not have scale problems.
The U.S.4 of Yin Ruing as mentioned, 163,728 is described, and metal base and acid-respons obtain product, obtain and the metal-salt bonded metal oxide of acid or the particulate of carbonate through decomposing.These particulates are suspended by the metal-salt of acid immediately and are stable.The particle diameter of metal oxide or carbonate is not more than 2 microns, and for example diameter is not more than 1 micron, is preferably and is not more than 0.1 micron, particularly should be less than 0.1 micron.
The scale inhibitor consumption that suppresses fouling in the dirt district is according to the degree of the environment in zone, fouling and the scale inhibitor that adopted and different.In general, in a zone, use the quantity of scale inhibitor should be able to suppress fouling effectively.Therefore, according to concrete environment, the consumption of scale inhibitor is approximately the 5ppm to 1000ppm that accounts for hydrocarbon stream weight or higher.Generally be approximately 25ppm to 500ppm, preferably be approximately 50ppm to 300ppm.
Claims (7)
1, the method that suppresses fouling in the refining of petroleum technology, this method comprises the scale inhibitor that add to suppress the fouling significant quantity to said technology (except that viscosity breaking plant) fouling position, and described scale inhibitor contains the high alkaline complex of (A) a kind of magnesium oxide and fatty acid magnesium salt and (B) high alkaline complex of a kind of magnesiumcarbonate and sulfonic acid magnesium salts.
2, the described method of claim 1, the lipid acid acid that wherein said lipid acid is Yatall MA.
3, the method that suppresses fouling in the gas complete processing, this method comprises the scale inhibitor that add to suppress the fouling significant quantity to said technology fouling position, and described scale inhibitor contains the high alkaline complex of (A) a kind of magnesium oxide and fatty acid magnesium salt and (B) high alkaline complex of a kind of magnesiumcarbonate and sulfonic acid magnesium salts.
4, the described method of claim 3, wherein said lipid acid is the lipid acid of Yatall MA.
5, the method that suppresses fouling in the petroleum chemistry complete processing, this method comprises the scale inhibitor that add to suppress the fouling significant quantity to said technology fouling position, and described scale inhibitor contains the high alkaline complex of (A) a kind of magnesium oxide and fatty acid magnesium salt and (B) high alkaline complex of a kind of magnesiumcarbonate and sulfonic acid magnesium salts.
6, the described method of claim 5, wherein said lipid acid is the lipid acid of Yatall MA.
7, antifouland compositions comprises the high alkaline complex of (A) a kind of magnesium oxide and fatty acid magnesium salt and (B) high alkaline complex of a kind of magnesiumcarbonate and sulfonic acid magnesium salts.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US91382186A | 1986-09-30 | 1986-09-30 | |
| US913.821 | 1986-09-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN87106648A true CN87106648A (en) | 1988-05-18 |
Family
ID=25433613
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN198787106648A Pending CN87106648A (en) | 1986-09-30 | 1987-09-30 | Blended overbase complex antifouland compositions and application thereof |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0267673A1 (en) |
| JP (1) | JPS63146988A (en) |
| KR (1) | KR880004069A (en) |
| CN (1) | CN87106648A (en) |
| AU (1) | AU577983B2 (en) |
| BR (1) | BR8704778A (en) |
| DE (1) | DE267673T1 (en) |
| ES (1) | ES2008054A4 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5034114A (en) * | 1989-07-28 | 1991-07-23 | Ira Kukin | Acid neutralizing combustion additive with detergent builder |
| US20100038289A1 (en) * | 2008-08-15 | 2010-02-18 | Exxonmobil Research And Engineering Company | Metal sulphonate additives for fouling mitigation in petroleum refinery processes |
| US8518238B2 (en) | 2009-04-09 | 2013-08-27 | General Electric Company | Processes for inhibiting fouling in hydrocarbon processing |
| JP5660654B2 (en) * | 2009-05-28 | 2015-01-28 | 伯東株式会社 | Method to prevent soil growth in the gas phase inside an oil quench tower |
| US8672019B1 (en) | 2012-12-27 | 2014-03-18 | Berndorf Band Gmbh | Cleaning unit for a continuous metal strip as well as a strip casting installation with such a cleaning unit |
| CN112209797B (en) * | 2019-07-10 | 2022-07-08 | 中国石油化工股份有限公司 | Method for inhibiting butter formation in olefin production from oxygen-containing compound, and butter inhibitor composition |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3328284A (en) * | 1965-01-06 | 1967-06-27 | Petrolite Corp | Oxyalkylate-sulfonate hydrocarbon inhibitor |
| DE267674T1 (en) * | 1986-09-30 | 1989-08-24 | Petrolite Corp., St. Louis, Mo. | COMPOSITIONS FOR PREVENTING INCRUSTINGS AND THEIR USE. |
-
1987
- 1987-09-04 EP EP87307862A patent/EP0267673A1/en not_active Withdrawn
- 1987-09-04 ES ES87307864T patent/ES2008054A4/en active Pending
- 1987-09-04 DE DE198787307862T patent/DE267673T1/en active Pending
- 1987-09-16 BR BR8704778A patent/BR8704778A/en unknown
- 1987-09-25 JP JP62239122A patent/JPS63146988A/en active Pending
- 1987-09-25 KR KR870010638A patent/KR880004069A/en not_active Application Discontinuation
- 1987-09-28 AU AU79046/87A patent/AU577983B2/en not_active Ceased
- 1987-09-30 CN CN198787106648A patent/CN87106648A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0267673A1 (en) | 1988-05-18 |
| BR8704778A (en) | 1988-05-17 |
| DE267673T1 (en) | 1989-08-24 |
| AU577983B2 (en) | 1988-10-06 |
| ES2008054A4 (en) | 1989-07-16 |
| JPS63146988A (en) | 1988-06-18 |
| AU7904687A (en) | 1988-03-03 |
| KR880004069A (en) | 1988-06-01 |
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