CN102527299A - Sulfonation reaction device and application thereof - Google Patents
Sulfonation reaction device and application thereof Download PDFInfo
- Publication number
- CN102527299A CN102527299A CN2010106094343A CN201010609434A CN102527299A CN 102527299 A CN102527299 A CN 102527299A CN 2010106094343 A CN2010106094343 A CN 2010106094343A CN 201010609434 A CN201010609434 A CN 201010609434A CN 102527299 A CN102527299 A CN 102527299A
- Authority
- CN
- China
- Prior art keywords
- sulfonation
- acid
- oil
- reaction
- sulphonator
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a sulfonation reaction device and an application thereof. The sulfonation reaction device consists of a gas-liquid separating tank, a sulfonation raw material tank, a sulfonation raw material pump, a sulfonator with a cooling and heat-preserving jacket, a horizontal decanter centrifuge, a circulating reflux pump, an aging tank, a neutralizing tank and an extracting tank, wherein the sulfonation raw material pump is connected with the sulfonation raw material tank and the sulfonator; the gas-liquid separating tank is connected with the sulfonator; the circulating reflux pump is arranged on a connecting circulating reflux pipeline in front of the sulfonation raw material pump and behind the horizontal decanter centrifuge; the other end of the sulfonator is connected with the horizontal decanter centrifuge; the aging tank is connected with the sulfonation oil outlet of the horizontal decanter centrifuge; the aging tank is connected with the neutralizing tank and the extracting tank; and the sulfonator is formed by hermetically connecting 2-8 glass tubes or metal tubes which are phi 22-27/phi 8-12 in outer diameter/inner diameter and are 100-500 millimeters in length. According to the sulfonation reaction device, a production process is quick and stable, continuous production is performed, and the tension of an oil-water interface can be below 1*10<-2> mN/m when the concentration of sulfonate is 0.1-0.3 percent.
Description
Technical field
The present invention relates to a kind of sulfonation reaction device and application process thereof, more particularly, relate to a kind of process units and application process thereof of petroleum sulfonate.
Background technology
Sulfonating reaction is that sulfonic group is introduced the reaction in the organic molecule.In the sulfonating reaction process, sulfonic sulphur atom is connected with carbon atom in the organic molecule, and the product that obtains is a sulfoacid compound.Common sulfonating reaction has benzene and derivative sulfonation, naphthalene and derivative sulfonation thereof, anthraquinone sulfonation, saturated and unsaturated aliphatic hydrocarbon sulfonation etc.The method of sulfonating that adopts in the industry mainly contains Sulphurex process, excess sulfuric acid sulfonation method, chlorosulfonic acid sulfonation method, sulphite sulfonation method, azeotropic anhydrate sulfonation method, baking process etc.The side reaction of sulfuric acid sulfonation method is many, and can produce a large amount of spent acid in the course of reaction; Chlorosulfonic acid sulfonation method production cost is very high; Sulphite sulfonation method, azeotropic ranges of application such as sulfonation method and the baking process limitation of anhydrating; Sulphurex process can be divided into gaseous sulfur trioxide sulfonation method and liquid sulphur trioxide sulfonation method by the sulfonating agent type.Adopt gaseous sulfur trioxide to make sulfonating agent, can be owing to have the actual amount of sulfur trioxide in the course of reaction near theoretical consumption, reaction is fast; Do not produce waste water, spent acid, equipment is not had corrosion, " three wastes " are few; Help advantages such as environmental protection, become consistent in the world advanced process for sulfonation of generally acknowledging, and obtain the industrialization promotion application; But because sulfur trioxide is too active, cause reaction violent, moment thermal discharge big; Cause phenomenons such as hot-spot, many sulfonation, oxidation and coking, thereby on equipment and technology, must take appropriate measures; Adopt liquid sulphur trioxide to react as sulfonating agent; Its advantage is that course of reaction does not produce spent acid; Post processing is simple, and product yield is high, and shortcoming is that the excessive oleum method of sulfonation of by-product sulfone analogy of this method generation is many; Only be applicable to inactive aromatic sulfonation, and requirement is sulfonated thing and sulfonated products is not too sticky liquid under reaction temperature.
On the mode of production, SO 3 sulfonated mode can be divided into three kinds of injecting type, membrane type and still formulas.The raw materials used overwhelming majority of membrane type method is the corresponding distillate of heavy alkyl benzene, heavy alkyl benzene cut or process refinement treatment; If petroleum distillate is without refining, the acid sludge that in sulfonation process, produces can stop up sulphonator, influences carrying out smoothly of sulfonation.It is more that still formula method is used to produce petroleum sulfonate, but shortcoming is that the reaction time is longer, and accessory substance is more; The injecting type method is for fraction oil of petroleum, and particularly colloid, the higher distillate of asphalt content are because the acid sludge that forms is more; Be prone to stop up playpipe or install other pipeline, influence is produced, when device is stopped work simultaneously; Sulfur trioxide waste gas, waste water or acid sludge possibly leak, contaminated environment.
CN1472199A adopts the continuous tank type sulfonation method, owing to adopt organic solvent as diluent, certainly will will increase solvent recovering system; Simultaneously in the sulfonating reaction process; Need the control reaction temperature in-30～30 ℃ of scopes, needing increases cooling system, has increased the production cost of sulfonate.In addition in process of production, owing to use a large amount of poisonous and harmful solvents, operating personnel and environment are worked the mischief.
CN1275431A, the disclosed sulfur trioxide membrane-type sulfonation of CN1203935A all adopt same sulfonation reactor to react for different material oil, and the oversulfonate phenomenon appears in this raw material that just might cause; Thereby the acid sludge that forms is too much; If the acid sludge that forms simultaneously in time separates, acid sludge can stick to tube wall, long-play meeting blocking pipe; Thereby influence the sulfonation effect, cause the sulfonate quality of generation unstable.
CN1275431 has reported the method with membrane-type sulfonation method sulfonated petroleum cut, and owing to arene content 12.4%, saturated hydrocarbon content 80.0% in the feedstock oil, but the sulfonated bodies amount seldom, and major part has been the difficult sulfonation saturated hydrocarbons of solvent action, thereby the sulfonate yield is not high.But if but the aromatics conversion rate of sulfonation was greater than 40% o'clock in the feedstock oil, and the acid sludge amount can be up to 4～9%, and last handling process is comparatively loaded down with trivial details.
CN1690025A adopts still formula sulfonation technology; The serial connection horizontal screw centrifuge separates a large amount of acid sludges that produce in the sulfonation process after utilizing the sulfonating reaction still; Acid sludge obstruction reactor and pipe problems that still formula sulfonating reaction produces have been solved; And reaction is carried out continuously, but the reaction time in the still formula sulfonation technology is longer, and the more problem of accessory substance still exists.
Summary of the invention
In sulfonation process, be prone to the acid sludge that oversulfonate phenomenon and reaction generate and can not get timely separation problem for solving existing membrane-type sulfonation device; Make the sulfonate quality of generation meet corresponding index request simultaneously, promptly the interfacial tension of the aqueous solution of 0.3% sulfonate and crude oil is 10
-3MN/m (SY/T5370-1999), one of the object of the invention is to provide a kind of sulfonation reaction device, and this device adopts length-adjustable sulfonation reactor; And partly sulfonated reaction mass carried out circulating reflux; Control the sulfonating reaction degree of depth, and the horizontal screw centrifuge through connecting thereafter, the acid sludge of generation is in time separated; Sulfonating reaction is carried out smoothly, can guarantee the sulfonate product quality problems again.
Two of the object of the invention is to provide the application process of above-mentioned sulfonation reaction device.This device adopts membrane type gaseous sulfur trioxide sulfonation technology that petroleum distillate is carried out sulfonation; The course of reaction quick and stable, the acid sludge amount of generation is in time separated, can serialization production; The sulfonate constituent mass of preparing as in ternary or the binary combination flooding finish is good, stable performance.
One of technical scheme provided by the invention is a sulfonation reaction device; By knockout drum, sulfonation head tank, the sulfonation feedstock pump of serial connection, have the sulphonator, horizontal screw centrifuge, circulation return pipe, ageing can, neutralizing tank, the extractor that cool off insulation jacket and form; The sulfonation feedstock pump connects sulfonation head tank and sulphonator; Knockout drum connects sulphonator, and before circulation return pipe is installed in the sulfonation feedstock pump, on the connection circulating reflux pipeline behind the horizontal screw centrifuge, the other end of sulphonator is connected with horizontal screw centrifuge; Ageing can is connected with the sulfonated oil outlet of horizontal screw centrifuge, and ageing can is connected with neutralizing tank, extractor successively.
Because petroleum distillate; Particularly colloid, when the higher distillate of asphalitine carries out sulfonating reaction as feedstock oil; If sulphonator is long, the acid sludge of generation meeting blocking pipe, sulphonator is short; The sulfonate non-conformity of quality that generates closes corresponding index, and promptly the interfacial tension of the aqueous solution of 0.1～0.3% sulfonate and crude oil is 10
-3MN/m (analytical method SY/T5370-1999) therefore needs sulphonator length is selected.Sulphonator of the present invention is made up of the glass tube or the metal tube of 2～8 φ, 22～27/ φ 8～12 (external diameter/internal diameter) * 100～500mm (length) sealing serial connection, can control the sulfonating reaction degree of depth according to the length that different raw materials is regulated sulphonator.
Described circulating reflux pipeline and sulfonation bore are complementary, and the circulating reflux bore is φ 8～12mm, and its internal diameter should be identical with the sulphonator internal diameter, be connected the sulfonation feedstock pump by circulation return pipe before, carry out the part circulating reflux, control the sulfonating reaction degree of depth.
The horizontal screw centrifuge of connecting behind the described sulphonator, the acid sludge that sulfonating reaction is generated in time obtain separating.Used horizontal screw centrifuge is commercially available prod, adapted as the case may be.
Two of technical scheme provided by the invention is the application of above-mentioned sulfonating reaction.The sulfonation raw material gets into sulphonator after the metering of sulfonation feedstock pump, sulfur trioxide gets into sulphonator behind the knockout drum separatory, the raw materials components mole ratio and the sulfonating reaction temperature of control sulfonation raw material and sulfur trioxide, and the reaction heat that sulfonating reaction is emitted can be removed with cooling water.The sulfonating reaction mixture is behind horizontal screw centrifuge, and isolated liquid partly is to deliver to ageing can after the circulation of sulfonation acid-soluble oil, and gas discharges behind exhaust treatment system, and acid sludge effluxes.
Gaseous sulfur trioxide accounts for sulfur trioxide and mixes 1～10% of back admixture of gas cumulative volume with air, and mixed admixture of gas carries out sulfonating reaction through getting in the sulfonation reactor behind the knockout drum separatory with the sulfonation raw material; Aromatic hydrocarbons and sulfur trioxide mol ratio in the control sulfonation raw material are 0.2～1: 1, and sulfonation temperature is 45～65 ℃, after the mixture process horizontal screw centrifuge after the sulfonating reaction is centrifugal; Acid sludge effluxes, and the sulfonation acid-soluble oil part circulating reflux after centrifugal, capacity of returns are 0～50% of the acid oil volume of sulfonation; The acid number of control sulfonation acid-soluble oil is 13～30mgKOH/g, gets into ageing can aging 1～3 hour, 65 ℃ of aging temperatures; The acid-soluble oil that obtains gets into neutralizing tank, use volumetric concentration be 20～50% sodium hydrate aqueous solution to be neutralized to pH be 7～9,40～90 ℃ of neutral temperatures; Neutralized reaction product gets into extractor again, and using volumetric concentration is the extraction of 20% ethanol water, and the ethanol water consumption is 10～40% of a neutralized reaction product volume; 40～90 ℃ of extraction temperature; 2 hours extraction time, be heated to 100 ℃ of concentrated 30min steam desolventize after, obtain active matter content greater than 35% petroleum sulfonate.
Sulfonation reactor adopts φ 22～27/ φ 8～12 (external diameter/internal diameter) * 100～500mm (length) glass tube or metal tube, is formed by 2-8 root glass tube or metal tube serial connection as required.Horizontal screw centrifuge of series connection behind the sulfonation reactor, centrifuge is commercially available horizontal screw centrifuge, in time separates the acid sludge that generates, and reactant circulates or partial reflux as required, and sulfur trioxide and feedstock oil adopt the concurrent hybrid reaction.Sulfonation is after the material of overaging through after neutralization, extracting, obtains the mahogany acid product salt behind the evaporating solvent.Enter atmosphere after the processing of waste gas entering exhaust treatment system is qualified.
Described sulfonation technology is the membrane-type sulfonation technology; Sulfonating agent is a gaseous sulfur trioxide; The sulfonation raw material be cycloalkyl, paraffinic base, intermediate base, aromatic radical second line of distillation, subtract three-way, subtract four lines and decompression residuum any one, the representative property scope of sulfonation raw material is seen table 1.
Table 1 sulfonation feedstock property
Because existing patent length to sulfonation reactor when carrying out the sulfur trioxide membrane-type sulfonation does not add restriction and unadjustable; This just might cause the oversulfonate phenomenon to some feedstock oil, thereby the acid sludge that forms is too much, and the acid sludge that forms simultaneously is not because of in time separating; Acid sludge is sticked on the tube wall; Long-play will certainly blocking pipe, and too much acid sludge can influence the sulfonation effect, causes the sulfonate quality of generation unstable.The present invention through adopting length-adjustable film sulfonation reactor, and carries out circulating reflux to partly sulfonated reaction mass just on existing process for sulfonation basis, controls the sulfonating reaction degree of depth, thereby has widened the range of choice of sulfonation raw material; Horizontal screw centrifuge through connecting thereafter in time separates the acid sludge of generation, has solved because of the acid sludge blocking pipe, influences the sulfonation effect problem, and whole process of production quick and stable of the present invention not only can be carried out serialization production, has also guaranteed the sulfonate product quality.The petroleum sulfonate of being produced by petroleum distillate is in the finite concentration scope, and oil water interfacial tension can reach the requirement of ternary or two yuan of combination floodings, and promptly the concentration of sulfonate was at 0.1～0.3% o'clock, and oil water interfacial tension can reach 1 * 10
-2Below the mN/m.
Description of drawings
Fig. 1 is sulfonation reaction device figure.
Wherein: 1, knockout drum 2, extractor 3, neutralizing tank 4, ageing can 5,6, sulphonator 7, horizontal screw centrifuge 8, sulfonation feedstock pump 9, sulfonation head tank
The specific embodiment
Sulfonation reaction device of the present invention by knockout drum 1, sulfonation head tank 9, the sulfonation feedstock pump 8 of serial connection, have the sulphonator 6, horizontal screw centrifuge 7, circulation return pipe 5, ageing can 4, neutralizing tank 3, the extractor 2 that cool off insulation jacket and form; Sulfonation feedstock pump 8 connects sulfonation head tank 9 and sulphonator 6; Knockout drum 1 connects sulphonator 6; Before circulation return pipe 5 is installed in the sulfonation feedstock pump, on the connection circulating reflux pipeline behind the horizontal screw centrifuge; The other end of sulphonator 6 is connected with horizontal screw centrifuge 7, and ageing can 4 is connected with the sulfonated oil outlet of horizontal screw centrifuge 7, and ageing can is connected with neutralizing tank 3, extractor 2 successively.
Sulphonator 6 is made up of the glass tube or the metal tube of 2～8 φ, 22～27/ φ 8～12 (external diameter/internal diameter) * 100～500mm (length) sealing serial connection.
The sulfonation feedstock oil that embodiment adopted be cycloalkyl, paraffinic base, intermediate base, aromatic radical second line of distillation, subtract three-way, subtract four lines and decompression residuum; Horizontal screw centrifuge is a horizontal spiral discharge sedimentation centrifuge, separating factor＜3600; Active matter content is measured and is adopted Q/LHY021-2007 standard, oil water interfacial tension to measure the SY/T5370-1999 standard that adopts.The mensuration of feedstock oil aromatic hydrocarbons adopts the SH/T0753-2005 standard.Acid value measuring adopts SH/T0092-1991 (2000) standard.
Embodiment 1
Cycloalkyl second line of distillation distillate: 359～410 ℃ of boiling ranges, colloid+asphalitine 7.24%, arene content C
A19.31%, 40 ℃ of viscosity 65.7mm
2/ s.
Cycloalkyl second line of distillation distillate gets into sulphonator after the metering of sulfonation feedstock pump; Account for sulfur trioxide mixes the back gained with air the sulfur trioxide gas of admixture of gas cumulative volume 3% and behind the knockout drum separatory, get into sulphonator; Carry out sulfonating reaction with sulfonation feedstock oil with concurrent; Sulfonation reactor is 8 of φ 22/ φ, 8 * 500 glass tubes or metal tubes; The raw materials components mole ratio of control loop alkyl second line of distillation distillate aromatic hydrocarbons and sulfur trioxide is 0.2: 1, and sulfonation temperature is 45 ℃, and the reaction heat that sulfonating reaction is emitted is removed with cooling water.The sulfonating reaction mixture is after horizontal screw centrifuge is centrifugal, and acid sludge effluxes, and the liquid that centrifugalizes out is sulfonation acid-soluble oil part circulating reflux; Capacity of returns is 0% of the acid oil volume of sulfonation, and the acid number of control sulfonation acid-soluble oil is 13mgKOH/g, and the sulfonation acid-soluble oil after circulating reflux is centrifugal got into ageing can aging 1 hour; 65 ℃ of aging temperatures, the acid-soluble oil that obtains get into neutralizing tank, and using volumetric concentration is that to be neutralized to pH be 7 to 20% sodium hydrate aqueous solution; 50 ℃ of neutral temperatures, neutralized reaction product gets into extractor again, and using volumetric concentration is the extraction of 20% ethanol water; The ethanolic solution consumption is 40% of a neutralized reaction product volume, 40 ℃ of extraction temperature, 2 hours extraction time; After the extracting and demixing ethanolic solution is separated; Remaining material keeps steaming in 30 minutes and obtains the mahogany acid product salt after removing ethanol water through being heated to 100 ℃, and this petroleum sulfonate product activity thing content is 60.74% (weight ratio), is 4.62 * 10 with the interfacial tension of distinguishing crude oil in its aqueous solution that is mixed with 0.1% sulfonate and the Kelamayi 7
-3MN/m.
Embodiment 2
Cycloalkyl subtracts three-way distillate: 382.1～448 ℃ of boiling ranges, colloid+asphalitine 8.1%, 21.86%, 40 ℃ of viscosity 287.1mm of aromatic hydrocarbons
2/ s, 210 ℃ of flash-points.
Cycloalkyl subtracts three-way distillate and after the metering of sulfonation feedstock pump, gets into sulphonator; Account for sulfur trioxide mixes the back gained with air the sulfur trioxide gas of admixture of gas cumulative volume 6% and behind the knockout drum separatory, get into sulphonator; Carry out sulfonating reaction with sulfonation feedstock oil with concurrent; Sulfonation reactor is 6 of φ 25/ φ 10 * 300 glass tubes; The raw materials components mole ratio that the control loop alkyl subtracts three-way distillate aromatic hydrocarbons and sulfur trioxide is 1: 1, and sulfonation temperature is 55 ℃, and the reaction heat that sulfonating reaction is emitted is removed with cooling water.The sulfonating reaction mixture is after horizontal screw centrifuge is centrifugal, and acid sludge effluxes, and the liquid that centrifugalizes out is sulfonation acid-soluble oil part circulating reflux; Capacity of returns is 30% of the acid oil volume of sulfonation, and the acid number of control sulfonation acid-soluble oil is 30mgKOH/g, and the sulfonation acid-soluble oil after circulating reflux is centrifugal got into ageing can aging 2 hours; 65 ℃ of aging temperatures, the acid-soluble oil that obtains get into neutralizing tank, and using volumetric concentration is that to be neutralized to pH be 8 to 20% sodium hydrate aqueous solution; 40 ℃ of neutral temperatures; Neutralized reaction product gets into extractor again, and using volumetric concentration is the extraction of 20% ethanol water, and the ethanolic solution consumption is 20% of a neutralized reaction product volume; 50 ℃ of extraction temperature; 2 hours extraction time, after the extracting and demixing ethanolic solution is separated, remaining material keeps steaming in 30 minutes to obtain the mahogany acid product salt except that behind the ethanol water through being heated to 100 ℃; This petroleum sulfonate product activity thing content is 52.38% (weight ratio), is 6.26 * 10 with its interfacial tension that is mixed with district's crude oil in the aqueous solution and the Kelamayi 7 of 0.3% sulfonate
-3MN/m.
Embodiment 3
Cycloalkyl subtracts four line distillates: 406.2～499.6 ℃ of boiling ranges, colloid+asphalitine 10.18%, 21.94%, 100 ℃ of viscosity 24.72mm of aromatic hydrocarbons
2/ s, 248 ℃ of flash-points.
Cycloalkyl subtracts four line distillates and after the metering of sulfonation feedstock pump, gets into sulphonator; Account for sulfur trioxide mixes the back gained with air the sulfur trioxide gas of admixture of gas cumulative volume 8% and behind gas-liquid jar separatory, get into sulphonator; Carry out sulfonating reaction with sulfonation feedstock oil with concurrent; Sulfonation reactor is 4 of φ 27/ φ 12 * 500 metal tubes; The raw materials components mole ratio that the control loop alkyl subtracts four line distillate aromatic hydrocarbons and sulfur trioxide is 0.5: 1, and sulfonation temperature is 65 ℃, and the reaction heat that sulfonating reaction is emitted is removed with cooling water.The sulfonating reaction mixture is after horizontal screw centrifuge is centrifugal, and acid sludge effluxes, and the liquid that centrifugalizes out is sulfonation acid-soluble oil part circulating reflux; Capacity of returns is 50% of the acid oil volume of sulfonation, and the acid number of control sulfonation acid-soluble oil is 20mgKOH/g, and the sulfonation acid-soluble oil after circulating reflux is centrifugal got into ageing can aging 3 hours; 65 ℃ of aging temperatures, the acid-soluble oil that obtains get into neutralizing tank, and using volumetric concentration is that to be neutralized to pH be 9 to 20% sodium hydrate aqueous solution; 60 ℃ of neutral temperatures; Neutralized reaction product gets into extractor again, and using volumetric concentration is the extraction of 50% ethanol water, and the ethanolic solution consumption is 10% of a neutralized reaction product volume; 60 ℃ of extraction temperature; 2 hours extraction time, after the extracting and demixing ethanolic solution is separated, remaining material keeps steaming in 30 minutes to obtain the mahogany acid product salt except that behind the ethanol water through being heated to 100 ℃; This petroleum sulfonate product activity thing content is 48.32% (weight ratio), is 7.43 * 10 with its interfacial tension that is mixed with district's crude oil in the aqueous solution and the Kelamayi 7 of 0.2% sulfonate
-3MN/m.
Embodiment 4
The cycloalkyl of boiling range＞520 ℃ subtracts slag through oversulfonate feedstock pump metering back entering sulphonator; Account for sulfur trioxide mixes the back gained with air the sulfur trioxide gas of admixture of gas cumulative volume 10% and behind the knockout drum separatory, get into sulphonator; Carry out sulfonating reaction with sulfonation feedstock oil with concurrent; Sulfonation reactor is 2 of φ 27/ φ 12 * 100 glass tubes; The raw materials components mole ratio that the control loop alkyl subtracts slag aromatic hydrocarbons and sulfur trioxide is 1: 1, and sulfonation temperature is 65 ℃, and the reaction heat that sulfonating reaction is emitted is removed with cooling water.The sulfonating reaction mixture is after horizontal screw centrifuge is centrifugal, and acid sludge effluxes, and the liquid that centrifugalizes out is sulfonation acid-soluble oil part circulating reflux; Capacity of returns is 10% of the acid oil volume of sulfonation, and the acid number of control sulfonation acid-soluble oil is 18mgKOH/g, and the sulfonation acid-soluble oil after the circulating reflux got into ageing can aging 1 hour; 65 ℃ of aging temperatures, the acid-soluble oil that obtains get into neutralizing tank, and using volumetric concentration is that to be neutralized to pH be 7 to 20% sodium hydrate aqueous solution; 80 ℃ of neutral temperatures, neutralized reaction product gets into extractor again, and using volumetric concentration is the extraction of 30% ethanol water; The ethanolic solution consumption is 30% of a neutralized reaction product volume, 80 ℃ of extraction temperature, 2 hours extraction time; After the extracting and demixing ethanolic solution is separated; Remaining material keeps steaming in 30 minutes and obtains the mahogany acid product salt after removing ethanol water through being heated to 100 ℃, and this petroleum sulfonate product activity thing content is 50.59% (weight ratio), is 4.95 * 10 with the interfacial tension of distinguishing crude oil in its aqueous solution that is mixed with 0.3% sulfonate and the Kelamayi 7
-3MN/m.
Embodiment 5
Paraffinic base second line of distillation distillate: 342.6～422.5 ℃ of boiling ranges, colloid+asphalitine 4.23%, 9.96%, 40 ℃ of viscosity 64.7mm of aromatic hydrocarbons
2/ s, 183 ℃ of flash-points.
Paraffinic base second line of distillation distillate gets into sulphonator after the metering of sulfonation feedstock pump; Account for sulfur trioxide mixes the back gained with air the sulfur trioxide gas of admixture of gas cumulative volume 3% and behind the knockout drum separatory, get into sulphonator; Carry out sulfonating reaction with the sulfonation raw material, sulfonation reactor is 8 of φ 22/ φ 8 * 100 steel pipes, and the raw materials components mole ratio of control paraffinic base second line of distillation distillate aromatic hydrocarbons and sulfur trioxide is 0.8: 1; Sulfonation temperature is 45 ℃, and the reaction heat that sulfonating reaction is emitted is removed with cooling water.The sulfonating reaction mixture is after horizontal screw centrifuge is centrifugal, and acid sludge effluxes, and the liquid that centrifugalizes out is sulfonation acid-soluble oil part circulating reflux; Capacity of returns is 20% of the acid oil volume of sulfonation, and the acid number of control sulfonation acid-soluble oil is 14mgKOH/g, and the sulfonation acid-soluble oil after circulating reflux is centrifugal got into ageing can aging 1 hour; 65 ℃ of aging temperatures, the acid-soluble oil that obtains get into neutralizing tank, and using volumetric concentration is that to be neutralized to pH be 7 to 20% sodium hydrate aqueous solution; 90 ℃ of neutral temperatures; Neutralized reaction product gets into extractor again, and using volumetric concentration is the extraction of 40% ethanol water, and the ethanolic solution consumption is 40% of a neutralized reaction product volume; 90 ℃ of extraction temperature; 2 hours extraction time, after the extracting and demixing ethanolic solution is separated, remaining material keeps steaming in 30 minutes to obtain the mahogany acid product salt except that behind the ethanol water through being heated to 100 ℃; This petroleum sulfonate product activity thing content is 56.86% (weight ratio), is 5.74 * 10 with its interfacial tension that is mixed with district's crude oil in the aqueous solution and the Kelamayi 7 of 0.2% sulfonate
-3MN/m.
Embodiment 6
Paraffinic base subtracts three-way distillate: 387.1～438 ℃ of boiling ranges, colloid+asphalitine 8.52%, 9.56%, 40 ℃ of viscosity 284.1mm of aromatic hydrocarbons
2/ s, 214 ℃ of flash-points.
Paraffinic base subtracts three-way distillate and after the metering of sulfonation feedstock pump, gets into sulphonator; Account for sulfur trioxide mixes the back gained with air the sulfur trioxide gas of admixture of gas cumulative volume 6% and after gas-liquid separation, get into sulphonator; Carry out sulfonating reaction with sulfonation feedstock oil with concurrent; Sulfonation reactor is 6 of φ 27/ φ 12 * 200 glass tubes; The raw materials components mole ratio that the control paraffinic base subtracts three-way distillate aromatic hydrocarbons and sulfur trioxide is 0.5: 1, and sulfonation temperature is 55 ℃, and the reaction heat that sulfonating reaction is emitted is removed with cooling water.The sulfonating reaction mixture is after horizontal screw centrifuge is centrifugal, and acid sludge effluxes, and the liquid that centrifugalizes out is sulfonation acid-soluble oil part circulating reflux; Capacity of returns is 30% of the acid oil volume of sulfonation, and the acid number of control sulfonation acid-soluble oil is 25mgKOH/g, and the sulfonation acid-soluble oil after circulating reflux is centrifugal got into ageing can aging 2 hours; 65 ℃ of aging temperatures, the acid-soluble oil that obtains get into neutralizing tank, and using volumetric concentration is that to be neutralized to pH be 8 to 20% sodium hydrate aqueous solution; 80 ℃ of neutral temperatures; Neutralized reaction product gets into extractor again, and using volumetric concentration is the extraction of 50% ethanol water, and the ethanolic solution consumption is 20% of a neutralized reaction product volume; 80 ℃ of extraction temperature; 2 hours extraction time, after the extracting and demixing ethanolic solution is separated, remaining material keeps steaming in 30 minutes to obtain the mahogany acid product salt except that behind the ethanol water through being heated to 100 ℃; This petroleum sulfonate product activity thing content is 46.27% (weight ratio), is 7.89 * 10 with its interfacial tension that is mixed with district's crude oil in the aqueous solution and the Kelamayi 7 of 0.1% sulfonate
-3MN/m.
Embodiment 7
Paraffinic base subtracts four line distillates: 407.2～499.8 ℃ of boiling ranges, colloid+asphalitine 8.18%, 11.24%, 100 ℃ of viscosity 26.82mm of aromatic hydrocarbons
2/ s, 257 ℃ of flash-points.
Paraffinic base subtracts four line distillates and after the metering of sulfonation feedstock pump, gets into sulfonation reactor; Account for sulfur trioxide mixes the back gained with air the sulfur trioxide gas of admixture of gas total volume concentration 8% and behind the knockout drum separatory, get into sulfonation reactor; Carry out sulfonating reaction with sulfonation feedstock oil with concurrent; Sulfonation reactor is 4 of φ 27/ φ 12 * 100 stainless steel tubes; The raw materials components mole ratio that the control paraffinic base subtracts four line distillate aromatic hydrocarbons and sulfur trioxide is 1: 1, and sulfonation temperature is 65 ℃, and the reaction heat that sulfonating reaction is emitted is removed with cooling water.The sulfonating reaction mixture is after horizontal screw centrifuge is centrifugal, and acid sludge effluxes, and the liquid that centrifugalizes out is sulfonation acid-soluble oil part circulating reflux; Capacity of returns is 30% of the acid oil volume of sulfonation, and the acid number of control sulfonation acid-soluble oil is 15mgKOH/g, and the sulfonation acid-soluble oil after circulating reflux is centrifugal got into ageing can aging 3 hours; 65 ℃ of aging temperatures, the acid-soluble oil that obtains get into neutralizing tank, and using volumetric concentration is that to be neutralized to pH be 9 to 20% sodium hydrate aqueous solution; 80 ℃ of neutral temperatures; Neutralized reaction product gets into extractor again, and using volumetric concentration is the extraction of 30% ethanol water, and the ethanolic solution consumption is 40% of a neutralized reaction product volume; 80 ℃ of extraction temperature; 2 hours extraction time, after the extracting and demixing ethanolic solution is separated, remaining material keeps steaming in 30 minutes to obtain the mahogany acid product salt except that behind the ethanol water through being heated to 100 ℃; This petroleum sulfonate product activity thing content is 49.64% (weight ratio), is 4.58 * 10 with its interfacial tension that is mixed with district's crude oil in the aqueous solution and the Kelamayi 7 of 0.3% sulfonate
-3MN/m.
Embodiment 8
Intermediate base subtracts three-way distillate: 387.1～438 ℃ of boiling ranges, colloid+asphalitine 8.52%, 19.56%, 40 ℃ of viscosity 284.1mm of aromatic hydrocarbons
2/ s, 214 ℃ of flash-points.
Intermediate base subtracts three-way distillate and after the metering of sulfonation feedstock pump, gets into sulfonation reactor; Account for sulfur trioxide mixes the back gained with air the sulfur trioxide gas of admixture of gas cumulative volume 6% and behind the knockout drum separatory, get into sulfonation reactor; Carry out sulfonating reaction with sulfonation feedstock oil with concurrent; Sulfonation reactor is 6 of φ 25/ φ 10 * 400 stainless steel tubes; The raw materials components mole ratio that the control intermediate base subtracts three-way distillate aromatic hydrocarbons and sulfur trioxide is 0.4: 1, and sulfonation temperature is 55 ℃, and the reaction heat that sulfonating reaction is emitted is removed with cooling water.The sulfonating reaction mixture is after horizontal screw centrifuge is centrifugal, and acid sludge effluxes, and the liquid that centrifugalizes out is sulfonation acid-soluble oil part circulating reflux; Capacity of returns is 30% of the acid oil volume of sulfonation, and the acid number of control sulfonation acid-soluble oil is 28mgKOH/g, and the sulfonation acid-soluble oil after circulating reflux is centrifugal got into ageing can aging 2 hours; 65 ℃ of aging temperatures, the acid-soluble oil that obtains get into neutralizing tank, and using volumetric concentration is that to be neutralized to pH be 8 to 20% sodium hydrate aqueous solution; 40 ℃ of neutral temperatures; Neutralized reaction product gets into extractor again, and using volumetric concentration is the extraction of 40% ethanol water, and the ethanolic solution consumption is 10% of a neutralized reaction product volume; 40 ℃ of extraction temperature; 2 hours extraction time, after the extracting and demixing ethanolic solution is separated, remaining material keeps steaming in 30 minutes to obtain the mahogany acid product salt except that behind the ethanol water through being heated to 100 ℃; This petroleum sulfonate product activity thing content is 63.43% (weight ratio), is 3.97 * 10 with its interfacial tension that is mixed with district's crude oil in the aqueous solution and the Kelamayi 7 of 0.1% sulfonate
-3MN/m.
Embodiment 9
Intermediate base subtracts four line distillates: 407.2～499.8 ℃ of boiling ranges, colloid+asphalitine 8.18%, 11.24%, 100 ℃ of viscosity 26.82mm of aromatic hydrocarbons
2/ s, 257 ℃ of flash-points.
Intermediate base subtracts four line distillates and after the metering of sulfonation feedstock pump, gets into sulphonator; Account for sulfur trioxide mixes the back gained with air the sulfur trioxide gas of admixture of gas total volume concentration 8% and behind the knockout drum separatory, get into sulphonator; Carry out sulfonating reaction with sulfonation feedstock oil with concurrent; Sulfonation reactor is 4 of φ 25/ φ 12 * 200 steel pipes; The raw materials components mole ratio that the control intermediate base subtracts four line distillate aromatic hydrocarbons and sulfur trioxide is 0.2: 1, and sulfonation temperature is 65 ℃, and the reaction heat that sulfonating reaction is emitted is removed with cooling water.The sulfonating reaction mixture is after horizontal screw centrifuge is centrifugal, and acid sludge effluxes, and the liquid that centrifugalizes out is sulfonation acid-soluble oil part circulating reflux; Capacity of returns is 50% of the acid oil volume of sulfonation, and the acid number of control sulfonation acid-soluble oil is 19mgKOH/g, and the sulfonation acid-soluble oil after circulating reflux is centrifugal got into ageing can aging 3 hours; 65 ℃ of aging temperatures, the acid-soluble oil that obtains get into neutralizing tank, and using volumetric concentration is that to be neutralized to pH be 9 to 20% sodium hydrate aqueous solution; 60 ℃ of neutral temperatures; Neutralized reaction product gets into extractor again, and using volumetric concentration is the extraction of 20% ethanol water, and the ethanolic solution consumption is 40% of a neutralized reaction product volume; 60 ℃ of extraction temperature; 2 hours extraction time, after the extracting and demixing ethanolic solution is separated, remaining material keeps steaming in 30 minutes to obtain the mahogany acid product salt except that behind the ethanol water through being heated to 100 ℃; This petroleum sulfonate product activity thing content is 52.47% (weight ratio), is 5.78 * 10 with its interfacial tension that is mixed with district's crude oil in the aqueous solution and the Kelamayi 7 of 0.2% sulfonate
-3MN/m.
Embodiment 10
The intermediate base of boiling range＞520 ℃ subtracts slag through oversulfonate feedstock pump metering back entering sulphonator; Account for sulfur trioxide mixes the back gained with air the sulfur trioxide gas of admixture of gas cumulative volume 10% and behind the knockout drum separatory, get into sulfonation reactor; Carry out sulfonating reaction with sulfonation feedstock oil with concurrent; Sulfonation reactor is 2 of φ 27/ φ 12 * 200 glass tubes; The raw materials components mole ratio that the control intermediate base subtracts slag aromatic hydrocarbons and sulfur trioxide is 0.9: 1, and sulfonation temperature is 65 ℃, and the reaction heat that sulfonating reaction is emitted is removed with cooling water.The sulfonating reaction mixture is after horizontal screw centrifuge is centrifugal, and acid sludge effluxes, and the liquid that centrifugalizes out is sulfonation acid-soluble oil part circulating reflux; Capacity of returns is 40% of the acid oil volume of sulfonation, and the acid number of control sulfonation acid-soluble oil is 23mgKOH/g, and the sulfonation acid-soluble oil after circulating reflux is centrifugal got into ageing can aging 1 hour; 65 ℃ of aging temperatures, the acid-soluble oil that obtains get into neutralizing tank, and using volumetric concentration is that to be neutralized to pH be 7 to 20% sodium hydrate aqueous solution; 60 ℃ of neutral temperatures; Neutralized reaction product gets into extractor again, and using volumetric concentration is the extraction of 50% ethanol water, and the ethanolic solution consumption is 20% of a neutralized reaction product volume; 60 ℃ of extraction temperature; 2 hours extraction time, after the extracting and demixing ethanolic solution is separated, remaining material keeps steaming in 30 minutes to obtain the mahogany acid product salt except that behind the ethanol water through being heated to 100 ℃; This petroleum sulfonate product activity thing content is 46.65% (weight ratio), is 6.32 * 10 with its interfacial tension that is mixed with district's crude oil in the aqueous solution and the Kelamayi 7 of 0.3% sulfonate
-3MN/m.
Embodiment 11
Aromatic radical second line of distillation distillate: 364.6～411.5 ℃ of boiling ranges, colloid+asphalitine 7.24%, 17.93%, 40 ℃ of viscosity 62.7mm of aromatic hydrocarbons
2/ s, 189 ℃ of flash-points.
Aromatic radical second line of distillation distillate gets into sulphonator after the metering of sulfonation feedstock pump; Account for sulfur trioxide mixes the back gained with air the sulfur trioxide gas of admixture of gas cumulative volume 3% and behind the knockout drum separatory, get into sulfonation reactor; Carry out sulfonating reaction with sulfonation feedstock oil with concurrent; Sulfonation reactor is 8 of φ 25/ φ 8 * 500 glass tubes; The raw materials components mole ratio of control aromatic radical second line of distillation distillate aromatic hydrocarbons and sulfur trioxide is 0.4: 1, and sulfonation temperature is 45 ℃, and the reaction heat that sulfonating reaction is emitted is removed with cooling water.The sulfonating reaction mixture is after horizontal screw centrifuge is centrifugal, and acid sludge effluxes, and the liquid that centrifugalizes out is sulfonation acid-soluble oil part circulating reflux; Capacity of returns is 10% of the acid oil volume of sulfonation, and the acid number of control sulfonation acid-soluble oil is 30mgKOH/g, and the sulfonation acid-soluble oil after circulating reflux is centrifugal got into ageing can aging 1 hour; 65 ℃ of aging temperatures, the acid-soluble oil that obtains get into neutralizing tank, and using volumetric concentration is that to be neutralized to pH be 7 to 20% sodium hydrate aqueous solution; 60 ℃ of neutral temperatures; Neutralized reaction product gets into extractor again, and using volumetric concentration is the extraction of 30% ethanol water, and the ethanolic solution consumption is 30% of a neutralized reaction product volume; 60 ℃ of extraction temperature; 2 hours extraction time, after the extracting and demixing ethanolic solution is separated, remaining material keeps steaming in 30 minutes to obtain the mahogany acid product salt except that behind the ethanol water through being heated to 100 ℃; This petroleum sulfonate product activity thing content is 68.38% (weight ratio), is 5.92 * 10 with its interfacial tension that is mixed with district's crude oil in the aqueous solution and the Kelamayi 7 of 0.3% sulfonate
-3MN/m.
Embodiment 12
Aromatic radical subtracts four line distillates: 410.2～493.5 ℃ of boiling ranges, colloid+asphalitine 10.18%, 27.94%, 100 ℃ of viscosity 25.56mm of aromatic hydrocarbons
2/ s, 253 ℃ of flash-points.
Aromatic radical subtracts four line distillates and after the metering of sulfonation feedstock pump, gets into sulphonator; Account for sulfur trioxide mixes the back gained with air the sulfur trioxide gas of admixture of gas cumulative volume 8% and behind the knockout drum separatory, get into sulphonator; Carry out sulfonating reaction with sulfonation feedstock oil with concurrent; Sulfonation reactor is 4 of φ 27/ φ 10 * 300 stainless steel tubes; The raw materials components mole ratio that the control aromatic radical subtracts four line distillate aromatic hydrocarbons and sulfur trioxide is 1: 1, and sulfonation temperature is 65 ℃, and the reaction heat that sulfonating reaction is emitted is removed with cooling water.The sulfonating reaction mixture is after horizontal screw centrifuge is centrifugal, and acid sludge effluxes, and the liquid that centrifugalizes out is sulfonation acid-soluble oil part circulating reflux; Capacity of returns is 40% of the acid oil volume of sulfonation, and the acid number of control sulfonation acid-soluble oil is 28mgKOH/g, and the sulfonation acid-soluble oil after circulating reflux is centrifugal got into ageing can aging 3 hours; 65 ℃ of aging temperatures, the acid-soluble oil that obtains get into neutralizing tank, and using volumetric concentration is that to be neutralized to pH be 9 to 20% sodium hydrate aqueous solution; 60 ℃ of neutral temperatures; Neutralized reaction product gets into extractor again, and using volumetric concentration is the extraction of 20% ethanol water, and the ethanolic solution consumption is 10% of a neutralized reaction product volume; 60 ℃ of extraction temperature; 2 hours extraction time, after the extracting and demixing ethanolic solution is separated, remaining material keeps steaming in 30 minutes to obtain the mahogany acid product salt except that behind the ethanol water through being heated to 100 ℃; This petroleum sulfonate product activity thing content is 53.57% (weight ratio), is 6.38 * 10 with its interfacial tension that is mixed with district's crude oil in the aqueous solution and the Kelamayi 7 of 0.3% sulfonate
-3MN/m.
Embodiment 13
The aromatic radical of boiling range＞520 ℃ subtracts slag through oversulfonate feedstock pump metering back entering sulfonation reactor; Account for sulfur trioxide mixes the back gained with air the sulfur trioxide gas of admixture of gas cumulative volume 10% and behind the knockout drum separatory, get into sulfonation reactor; Carry out sulfonating reaction with sulfonation feedstock oil with concurrent; Sulfonation reactor is 2 of φ 27/ φ 12 * 300 glass tubes; The raw materials components mole ratio that the control aromatic radical subtracts slag aromatic hydrocarbons and sulfur trioxide is 0.2: 1, and sulfonation temperature is 65 ℃, and the reaction heat that sulfonating reaction is emitted is removed with cooling water.The sulfonating reaction mixture is after horizontal screw centrifuge is centrifugal, and acid sludge effluxes, and the liquid that centrifugalizes out is sulfonation acid-soluble oil part circulating reflux; Capacity of returns is 20% of the acid oil volume of sulfonation, and the acid number of control sulfonation acid-soluble oil is 19mgKOH/g, and the sulfonation acid-soluble oil after circulating reflux is centrifugal got into ageing can aging 1 hour; 65 ℃ of aging temperatures, the acid-soluble oil that obtains get into neutralizing tank, and using volumetric concentration is that to be neutralized to pH be 7 to 20% sodium hydrate aqueous solution; 80 ℃ of neutral temperatures; Neutralized reaction product gets into extractor again, and using volumetric concentration is the extraction of 20% ethanol water, and the ethanolic solution consumption is 40% of a neutralized reaction product volume; 80 ℃ of extraction temperature; 2 hours extraction time, after the extracting and demixing ethanolic solution is separated, remaining material keeps steaming in 30 minutes to obtain the mahogany acid product salt except that behind the ethanol water through being heated to 100 ℃; This petroleum sulfonate product activity thing content is 51.39% (weight ratio), is 5.84 * 10 with its interfacial tension that is mixed with district's crude oil in the aqueous solution and the Kelamayi 7 of 0.3% sulfonate
-3MN/m.
Claims (4)
1. sulfonation reaction device; It is characterized in that: by knockout drum, sulfonation head tank, sulfonation feedstock pump, have the sulphonator, horizontal screw centrifuge, circulation return pipe, ageing can, neutralizing tank, the extractor that cool off insulation jacket and form; The sulfonation feedstock pump connects sulfonation head tank and sulphonator; Knockout drum connects sulphonator, and before circulation return pipe is installed in the sulfonation feedstock pump, on the connection circulating reflux pipeline behind the horizontal screw centrifuge, the other end of sulphonator is connected with horizontal screw centrifuge; Ageing can is connected with the sulfonated oil outlet of horizontal screw centrifuge, and ageing can is connected with neutralizing tank, extractor successively;
Described sulphonator is φ 22～27/ φ 8～12 by 2～8 external diameter/internal diameters, and length is 100～500mm glass tube or the metal tube composition that is tightly connected.
2. the application of the described sulfonation reaction device of claim 1; It is characterized in that: sulfonation feedstock oil gets into sulphonator after the metering of sulfonation feedstock pump, the sulfur trioxide gas that accounts for sulfur trioxide and air gas mixture cumulative volume 1～10% gets into sulphonator after the knockout drum separatory takes off liquid acid, carry out sulfonating reaction with sulfonation feedstock oil with concurrent; The raw materials components mole ratio of control sulfonation feedstock oil aromatic hydrocarbons and sulfur trioxide gas is 0.2～1: 1; Sulfonation temperature is 45～65 ℃, and the reaction heat that sulfonating reaction is emitted is removed with the type of cooling, and the sulfonating reaction mixture is after horizontal screw centrifuge is centrifugal; Acid sludge effluxes; The liquid that centrifugalizes out is sulfonation acid-soluble oil part circulating reflux, and capacity of returns is 0～50% of the acid oil volume of sulfonation, and the acid number of control sulfonation acid-soluble oil is 13～30mgKOH/g; Sulfonation acid-soluble oil after circulating reflux is centrifugal got into ageing can aging 1～3 hour, 65 ℃ of aging temperatures, and the acid-soluble oil that obtains gets into neutralizing tank; Use volumetric concentration be 20% sodium hydrate aqueous solution to be neutralized to pH be 7～9,40～90 ℃ of neutral temperatures, neutralized reaction product gets into extractor again; Using volumetric concentration is the extractions of 20～50% ethanol waters; The ethanolic solution consumption is 10～40% of a neutralized reaction product volume, 40～90 ℃ of extraction temperature, 2 hours extraction time; After the extracting and demixing ethanolic solution is separated, remaining material keeps steaming in 30 minutes to obtain the mahogany acid product salt except that behind the ethanol water through being heated to 100 ℃.
3. the application of sulfonation reaction device according to claim 2 is characterized in that: the second line of distillation that said sulfonation feedstock oil is cycloalkyl, paraffinic base, intermediate base, aromatic radical, subtract three-way, subtract four lines and decompression residuum any one.
4. the application of sulfonation reaction device according to claim 3 is characterized in that: in the said sulfonation feedstock oil, second line of distillation raw material boiling range is 340～430 ℃, C
A% is 5～20%, and colloid+asphalitine is not more than 10%; Subtracting three-way raw material boiling range is 370～480 ℃, C
A% is 5～35%, and colloid+asphalitine is not more than 15%; Subtracting four line raw material boiling ranges is 400～520 ℃, C
A% is 5～35%, and colloid+asphalitine is not more than 15%; The decompression residuum boiling range is greater than 520 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010106094343A CN102527299A (en) | 2010-12-17 | 2010-12-17 | Sulfonation reaction device and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010106094343A CN102527299A (en) | 2010-12-17 | 2010-12-17 | Sulfonation reaction device and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102527299A true CN102527299A (en) | 2012-07-04 |
Family
ID=46336053
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010106094343A Pending CN102527299A (en) | 2010-12-17 | 2010-12-17 | Sulfonation reaction device and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102527299A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104557622A (en) * | 2014-12-18 | 2015-04-29 | 中国石油天然气股份有限公司 | Sulfonation reaction method and device |
| CN109265376A (en) * | 2018-10-22 | 2019-01-25 | 中石油克拉玛依石化有限责任公司 | The method and device of continous way production petroleum sulfonate |
| CN111495289A (en) * | 2020-04-27 | 2020-08-07 | 肇庆市高要华新香料有限公司 | Gas-liquid two-phase continuous reaction device and preparation method of sorbol |
| CN114570323A (en) * | 2020-11-18 | 2022-06-03 | 中国石油天然气股份有限公司 | Preparation device and preparation method of petroleum sulfonate |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1272393A (en) * | 1999-04-30 | 2000-11-08 | 大庆石油管理局 | Alkyl benzene sulfonate surfactant, its preparation method and application in tertiary oil recovery |
| JP2001002633A (en) * | 1999-06-17 | 2001-01-09 | Lion Corp | PRODUCTION OF alpha-SULFOFATTY ACID ALKYL ESTER SALT AND SULFONATION APPARATUS THEREFOR |
| CN1690025A (en) * | 2004-04-29 | 2005-11-02 | 中国石油天然气股份有限公司 | Sulphonation reaction producing technology and equipment thereof |
| CN101099927A (en) * | 2006-07-06 | 2008-01-09 | 上海和黄白猫有限公司 | Dual-membrane type sulfur trioxide sulfonation reactor |
| JP2010202646A (en) * | 2009-02-04 | 2010-09-16 | Lion Corp | METHOD FOR PRODUCING alpha-SULFOFATTY ACID ALKYL ESTER SALT WITH REDUCED AMOUNT OF BY-PRODUCT |
-
2010
- 2010-12-17 CN CN2010106094343A patent/CN102527299A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1272393A (en) * | 1999-04-30 | 2000-11-08 | 大庆石油管理局 | Alkyl benzene sulfonate surfactant, its preparation method and application in tertiary oil recovery |
| JP2001002633A (en) * | 1999-06-17 | 2001-01-09 | Lion Corp | PRODUCTION OF alpha-SULFOFATTY ACID ALKYL ESTER SALT AND SULFONATION APPARATUS THEREFOR |
| CN1690025A (en) * | 2004-04-29 | 2005-11-02 | 中国石油天然气股份有限公司 | Sulphonation reaction producing technology and equipment thereof |
| CN101099927A (en) * | 2006-07-06 | 2008-01-09 | 上海和黄白猫有限公司 | Dual-membrane type sulfur trioxide sulfonation reactor |
| JP2010202646A (en) * | 2009-02-04 | 2010-09-16 | Lion Corp | METHOD FOR PRODUCING alpha-SULFOFATTY ACID ALKYL ESTER SALT WITH REDUCED AMOUNT OF BY-PRODUCT |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104557622A (en) * | 2014-12-18 | 2015-04-29 | 中国石油天然气股份有限公司 | Sulfonation reaction method and device |
| CN109265376A (en) * | 2018-10-22 | 2019-01-25 | 中石油克拉玛依石化有限责任公司 | The method and device of continous way production petroleum sulfonate |
| CN109265376B (en) * | 2018-10-22 | 2021-07-02 | 克拉玛依市先进能源技术创新有限公司 | Method and device for continuously producing petroleum sulfonate |
| CN111495289A (en) * | 2020-04-27 | 2020-08-07 | 肇庆市高要华新香料有限公司 | Gas-liquid two-phase continuous reaction device and preparation method of sorbol |
| CN111495289B (en) * | 2020-04-27 | 2021-01-12 | 肇庆市高要华新香料有限公司 | Gas-liquid two-phase continuous reaction device and preparation method of sorbol |
| CN114570323A (en) * | 2020-11-18 | 2022-06-03 | 中国石油天然气股份有限公司 | Preparation device and preparation method of petroleum sulfonate |
| CN114570323B (en) * | 2020-11-18 | 2023-09-26 | 中国石油天然气股份有限公司 | Petroleum sulfonate preparation device and preparation method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Gouveia et al. | Deep eutectic solvents as azeotrope breakers: liquid–liquid extraction and COSMO-RS prediction | |
| CN102527299A (en) | Sulfonation reaction device and application thereof | |
| Li et al. | Acid dicationic ionic liquids as extractants for extractive desulfurization | |
| US9096805B2 (en) | Anhydride demulsifier formulations for resolving emulsions of water and oil | |
| Yu et al. | Desulfurization of diesel fuel by one-pot method with morpholinium-based Brønsted acidic ionic liquid | |
| CN105176556A (en) | Method for separating phenol from coal tar phenol-containing distillate oil | |
| CN103864648B (en) | A kind of sulfonated aromatic diamine compound and preparation method thereof and application | |
| BR112016025211B1 (en) | tetraryl methane ethers for use as oil and fuel markers | |
| Yao et al. | Ternary phase behavior of phenol+ toluene+ zwitterionic alkaloids for separating phenols from oil mixtures via forming deep eutectic solvents | |
| CN102998429A (en) | Method for facilitating coal swelling by pyridine ionic liquids | |
| CN104403652A (en) | Preparation method of petroleum sulfonate surfactant for oil displacement | |
| Ayuso et al. | Cyclic carbonates as solvents in the dearomatization of refinery streams: Experimental liquid–liquid equilibria, modelling, and simulation | |
| Ibrahimova et al. | Selective purification of the oil fractions with use of ionic liquid as extractant on the basis of n-methyl pyrrolidone | |
| CN103724235A (en) | Aromatic raffinate oil sulfoacid, or aromatic raffinate oil sulfonate, and preparation method and application of aromatic raffinate oil sulfoacid | |
| US20190194449A1 (en) | Heavy oil demulsifier | |
| JP2015520270A (en) | Preparation of polymers of thiophene, benzothiophene, and their alkylated derivatives | |
| CN103450056A (en) | Mahogany petroleum sulfonate preparation method for oil exploitation | |
| CN111218301A (en) | Extraction solvent for deep desulfurization of sulfur-containing raw material | |
| CN103508866B (en) | A kind of synthesis technique of salicylic aldehyde | |
| CN103951009A (en) | Coking demulsifier and preparation method thereof | |
| CN115584278A (en) | Special low-temperature environment-friendly anti-corrosive demulsifier for aging oil | |
| US2927076A (en) | Stabilizing sulfonated petroleum with organic sulfoxides | |
| CN109265376A (en) | The method and device of continous way production petroleum sulfonate | |
| Pardee et al. | The Influence of Ester Transposition in the Determination of Saponification Numbers | |
| US2578657A (en) | Process for producing sulfonic acids and sulfonates |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120704 |