CN104557622B - Sulfonation reaction method and device - Google Patents
Sulfonation reaction method and device Download PDFInfo
- Publication number
- CN104557622B CN104557622B CN201410797837.3A CN201410797837A CN104557622B CN 104557622 B CN104557622 B CN 104557622B CN 201410797837 A CN201410797837 A CN 201410797837A CN 104557622 B CN104557622 B CN 104557622B
- Authority
- CN
- China
- Prior art keywords
- sulfonation
- spiral coil
- temperature
- sulfonation mixture
- raw oil
- 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.)
- Active
Links
Abstract
The invention provides a sulfonation reaction method and device. The method comprises the following steps: injecting constant-temperature circulating water to keep the temperature in a reaction kettle at 27-60 DEG C, thereby keeping the state of the liquid sulfur trioxide stable; uniformly spraying raw oil and the liquid sulfur trioxide while controlling the ratio of the first flow rate of the raw oil to the second flow rate of the liquid sulfur trioxide at 15:1-30:1, and enabling the raw oil and liquid sulfur trioxide to form a fog film overlay area and generate primary sulfonation reaction, thereby obtaining a primary sulfonation mixture; carrying out primary cooling on the primary sulfonation mixture to control the temperature of the primary sulfonation mixture at 30-60 DEG C; mixing the primary sulfonation mixture with a filler to carry out secondary sulfonation reaction, thereby obtaining a secondary sulfonation mixture; carrying out secondary cooling on the secondary sulfonation mixture to control the temperature of the secondary sulfonation mixture at 30-60 DEG C; and carrying out aging and neutralization on the secondary sulfonation mixture to obtain the petroleum sulfonate product. Thus, the heat dissipation effect of the sulfonation reaction is enhanced.
Description
Technical field
The invention belongs to technical field of petrochemical industry, more particularly, to a kind of sulfonating reaction method and device.
Background technology
At present, conventional sulfonation reactor has：Autoclave, pot group type, membrane type and injection-type reactor.For liquid three oxygen
Change sulphur vulcanization reactor and mostly adopt autoclave and pot group type, but both reactors all have material back-mixing seriously, by-product
The many and uneven problem of product quality.Additionally, liquid sulphur trioxide typically first passes through organic solvent diluting, then with raw material oily hair
Raw sulfonating reaction, is then passed through the steps such as neutralization, separating-purifying and obtains mahogany acid product salt.But due to using in sulfonation process
To organic solvent, endanger environment.
The supergravity reactor developed in recent years, has been successfully applied in the synthesis of petroleum sulfonate although this reactor
High-gravity technology is introduced in the sulfonating reaction of sulfur trioxide, enhances reactant micro mixing, overcome autoclave and tank
The problem that in group formula sulfonation reactor, material back-mixing is serious and quality is uneven, but it is because sulfan sulfonation ability very
By force, react acutely, temperature rapidly rises, if having little time radiating it is easy to generate sulfone to wait sulfonated products；And hypergravity reaction
Device is still radiated using the ordinary cycle set type of cooling, and radiating effect is poor, the problem of coking easily.
Content of the invention
The problem existing for prior art, embodiments provides a kind of sulfonation reaction device and method, is used for
In solution prior art, sulfonating reaction radiating effect is poor, the problem of coking easily.
The invention provides a kind of sulfonating reaction method, methods described includes：
Injection thermostatical circulating water, the temperature in reactor is maintained at 27-60 DEG C, stablizes the state of liquid sulphur trioxide；
Uniformly spray raw oil and described liquid sulphur trioxide, control the first flow velocity of described raw oil and described liquid three
The ratio of the second flow speed of sulfur oxide is 15:1～30:1, make described raw oil form mist film overlay region with described liquid sulphur trioxide
, there is a sulfonating reaction, obtain a sulfonation mixture in domain；
A described sulfonation mixture is once lowered the temperature, controls the temperature of described sulfonated bodiess to be 30～60 DEG C；
Described sulfonated bodiess are mixed with filling filler, carries out secondary sulfonating reaction；
To described secondary sulfonation mixture reducing temperature twice, the temperature of described secondary sulfonated bodiess is controlled to be 30～60 DEG C；
Described secondary sulfonated bodiess are carried out with aging, neutralization reaction, obtains mahogany acid product salt.
In such scheme, described described secondary sulfonation mixture is once lowered the temperature, control described sulfonated bodiess temperature be 30
～60 DEG C of inclusions：
By injecting cooling water in the first spiral coil, described sulfonation mixture is once lowered the temperature, control described sulfonation
The temperature of thing is 30～60 DEG C.
Present invention also offers a kind of sulfonation reaction device, described device includes：
Muff, described muff is used for, by injecting thermostatical circulating water, the temperature in reactor being maintained at 27-60
DEG C, stablize the state of liquid sulphur trioxide；
Gondola water faucet, described gondola water faucet is used for uniform ejection raw oil；
Jet pipe, described jet pipe is used for uniformly spraying described liquid sulphur trioxide, by controlling the first of described raw oil
The ratio of flow velocity and the second flow speed of described liquid sulphur trioxide is 15:1～30:1, make described raw oil and the oxidation of described liquid three
Sulfur forms mist film overlapping region, a sulfonating reaction occurs, obtains a sulfonation mixture；
First spiral coil, described first spiral coil is used for a described sulfonation mixture is once lowered the temperature, and controls institute
The temperature stating sulfonated bodiess is 30～60 DEG C；
Packed bed；Described packed bed is used for mixing described sulfonated bodiess with filling filler, carries out secondary sulfonating reaction,
Obtain secondary sulfonation mixture；
Second spiral coil, described second spiral coil is used for, to described secondary sulfonation mixture reducing temperature twice, controlling institute
The temperature stating secondary sulfonated bodiess is 30～60 DEG C；
Neutralizing tank, described neutralizing tank is used for carrying out aging, neutralization reaction to described secondary sulfonated bodiess, obtains petroleum sulfonate
Product.
In such scheme, described device also includes：
First water inlet, described first water inlet is used for injecting described thermostatical circulating water in described muff；
First outlet, described first outlet is used for for described thermostatical circulating water flowing out described muff.
In such scheme, described device also includes：
Inlet, described inlet is used for injecting described raw oil in described gondola water faucet.
In such scheme, described device also includes：
Second water inlet, described second water inlet is used for injecting cooling water in described first spiral coil；
Second outlet, described second outlet is used for cooling water flow out of described first spiral coil by described.
In such scheme, described device also includes：
3rd water inlet, described 3rd water inlet is used for injecting cooling water in described second spiral coil；
3rd outlet, described 3rd outlet is used for cooling water flow out of described second spiral coil by described.
In such scheme, described second spiral coil includes：
Ground floor endless solenoid, described ground floor endless solenoid is arranged on the side of described packed bed；
Second layer endless solenoid, described second layer endless solenoid is arranged in described packed bed.
The invention provides a kind of sulfonating reaction method and device, methods described includes injecting thermostatical circulating water, will react
Temperature in kettle is maintained at 27-60 DEG C, stablizes the state of liquid sulphur trioxide；Uniformly spray raw oil and described liquid three aoxidizes
Sulfur, the ratio of the first flow velocity and the second flow speed of described liquid sulphur trioxide controlling described raw oil is 15:1～30:1, make institute
State raw oil and form mist film overlapping region with described liquid sulphur trioxide, a sulfonating reaction occurs, obtain sulfonation mixing
Thing；A described sulfonation mixture is once lowered the temperature, controls the temperature of described sulfonated bodiess to be 30～60 DEG C；By described once
Sulfonated bodiess are mixed with filling filler, carry out secondary sulfonating reaction, obtain secondary sulfonation mixture；To described secondary sulfonation mixture
Reducing temperature twice, controls the temperature of described secondary sulfonated bodiess to be 30～60 DEG C；Described secondary sulfonated bodiess are carried out with aging, neutralization anti-
Should, obtain mahogany acid product salt.So, radiating effect is improve using two-stage cooling system, decrease sulfonation process in temperature
The generation of by-product in the case of degree is higher, and the interfacial tension of the mahogany acid product salt obtaining is lower, meets tertiary oil recovery
Learn drive surfactant properties to require.
Brief description
Fig. 1 is liquid sulphur trioxide sulfonating reaction process schematic flow sheet provided in an embodiment of the present invention；
Fig. 2 is liquid sulphur trioxide sulfonation reaction device overall structure diagram provided in an embodiment of the present invention.
Specific embodiment
In order to solve the problems, such as the reaction poor and easy coking of radiating effect of liquid-liquid sulfonation synthetic petroleum sulfonate, this
Bright embodiment provides a kind of sulfonation reaction device and method, injects thermostatical circulating water, the temperature in reactor is maintained at 27-
60 DEG C, stablize the state of liquid sulphur trioxide；Uniformly spray raw oil and described liquid sulphur trioxide, control described raw oil
The ratio of the first flow velocity and the second flow speed of described liquid sulphur trioxide is 15:1～30:1, make described raw oil and described liquid three
Sulfur oxide forms mist film overlapping region, a sulfonating reaction occurs, obtains a sulfonation mixture；To described sulfonation mixing
Thing is once lowered the temperature, and controls the temperature of described sulfonated bodiess to be 30～60 DEG C；Described sulfonated bodiess are mixed with filling filler,
Carry out secondary sulfonating reaction, obtain secondary sulfonation mixture；To described secondary sulfonation mixture reducing temperature twice, control described secondary
The temperature of sulfonated bodiess is 30～60 DEG C；Described secondary sulfonated bodiess are carried out with aging, neutralization reaction, obtains mahogany acid product salt.
Below by drawings and the specific embodiments, technical scheme is described in further detail.
Embodiment one
Present embodiments provide a kind of sulfonating reaction method, as shown in figure 1, the method comprising the steps of：
Step 110, injects thermostatical circulating water, the temperature in reactor is maintained at 27-60 DEG C, stablizes liquid sulphur trioxide
State；
In this step, inject 27-40 DEG C of thermostatical circulating water into muff by the first water inlet, by reactor
Temperature be maintained at 27-60 DEG C, stablize the state of described liquid sulphur trioxide, it is to avoid described liquid sulphur trioxide is set in jet pipe
In.Described thermostatical circulating water passes through the first outlet and flows out described muff.
Step 111, uniformly sprays raw oil and described liquid sulphur trioxide, controls the first flow velocity and the institute of described raw oil
The ratio of second flow speed stating liquid sulphur trioxide is 15:1～30:1, make described raw oil form mist with described liquid sulphur trioxide
, there is a sulfonating reaction, obtain a sulfonation mixture in film overlapping region；
In this step, open described gondola water faucet and described jet pipe；By described inlet, raw oil is injected in described gondola water faucet,
Raw oil is uniformly sprayed by described gondola water faucet；Described liquid sulphur trioxide is uniformly sprayed by described jet pipe, controls described raw oil
The ratio of the first flow velocity and the second flow speed of described liquid sulphur trioxide is 15:1～30:1mL/min, make described raw oil with described
Liquid sulphur trioxide forms mist film overlapping region, a sulfonating reaction occurs, obtains a sulfonation mixture.
Step 112, once lowers the temperature to a described sulfonation mixture, and the temperature controlling described sulfonated bodiess is 30～60
℃；
In this step, after described sulfonation mixture successively reaches described first spiral coil, described first spiral coil
A described sulfonation mixture is once lowered the temperature, controls the temperature of described sulfonated bodiess to be 30～60 DEG C.
Specifically, described first spiral coil is can be passed through being coiled to form by center convolution of recirculated cooling water by one
Coil pipe is made, including：Second water inlet, the second outlet；Wherein,
Described second water inlet is used for injecting recirculated cooling water in described first spiral coil；Described second outlet 21
For described recirculated cooling water is flowed out described first spiral coil, once to be lowered the temperature to a described sulfonation mixture.
Step 113, described sulfonated bodiess is mixed with filling filler, carries out secondary sulfonating reaction, obtain secondary sulfonation
Mixture；
In this step, after a described sulfonation mixture leaves described first spiral coil, when reaching described packed bed,
Described packed bed is passed through rotation and is mixed described sulfonated bodiess with filling filler, carries out secondary sulfonating reaction, and strengthening was reacted
Journey, obtains secondary sulfonation mixture.
Step 114, to described secondary sulfonation mixture reducing temperature twice, the temperature controlling described secondary sulfonated bodiess is 30～60
℃；
In this step, during secondary sulfonating reaction, produced heat is taken away by described second spiral coil, to institute
State sulfonation mixture reducing temperature twice, control the temperature of described sulfonated bodiess to be 30～60 DEG C.Specifically, described second spiral coil is solid
It is scheduled in described RPB；By described 3rd water inlet, recirculated cooling water is injected in described second spiral coil；Logical
Cross described 3rd outlet and cooling water flow out of described second spiral coil by described, described secondary sulfonating reaction process is dropped
Temperature.
Described secondary sulfonated bodiess are carried out aging, neutralization reaction by step 115, obtain mahogany acid product salt；
In this step, after secondary sulfonating reaction terminates, sulfonated bodiess are pooled to the bottom of reactor, enter institute through discharging opening
State in neutralizing tank, described sulfonated bodiess carry out aging, neutralization reaction in described neutralizing tank, obtain mahogany acid product salt.
Embodiment two
Corresponding to embodiment one, present embodiments provide a kind of sulfonation reaction device, as shown in Fig. 2 described device includes：
Muff 11, gondola water faucet 12, jet pipe 13, the first spiral coil 14, packed bed 15, the second spiral coil 16, neutralizing tank 17, first enter
The mouth of a river 18, the first outlet 19, the second water inlet 20, the second outlet 21, the 3rd water inlet 22, the 3rd outlet 23, first
Inlet 24 and the second inlet 25；Wherein,
Described muff 11 passes through the thermostatical circulating water that described first water inlet 18 injects 27-40 DEG C, by reactor
26 temperature is maintained at 27-60 DEG C, stablizes the state of described liquid sulphur trioxide, it is to avoid described liquid sulphur trioxide is set in spray
In pipe 13.Described thermostatical circulating water flows out described muff 11 by the first outlet 19.
Open described gondola water faucet 12 and described jet pipe 13；Raw oil is injected by described gondola water faucet 12 by described first inlet 24
In, raw oil is uniformly sprayed by described gondola water faucet 12；Liquid sulphur trioxide is injected by described jet pipe by described second inlet 25
In 13, described liquid sulphur trioxide is uniformly sprayed by described jet pipe 13, controls the first flow velocity of described raw oil and described liquid
The ratio of the second flow speed of sulfur trioxide is 15:1～30:1mL/min, makes described raw oil form mist with described liquid sulphur trioxide
, there is a sulfonating reaction, obtain a sulfonation mixture in film overlapping region.
After described sulfonation mixture successively reaches described first spiral coil 14, described first spiral coil 14 is to described
One time sulfonation mixture is once lowered the temperature, and controls the temperature of described sulfonated bodiess to be 30～60 DEG C.
Specifically, described first spiral coil 14 is can be passed through recirculated cooling water by one, is become with center for round dot disk
Endless solenoid make, described first spiral coil 14 is close to the side of jet pipe 13；Including：Second water inlet 20, second
Outlet 21；Wherein,
Described second water inlet 20 is used for injecting recirculated cooling water in described first spiral coil 14；Described second water outlet
Mouth 21 is used for described recirculated cooling water being flowed out described first spiral coil 14, to carry out once to a described sulfonation mixture
Cooling.
After a described sulfonation mixture leaves described first spiral coil 14, reach described packed bed 15, described fill out
Fill bed 15 to mix described sulfonated bodiess with filling filler by rotation, carry out secondary sulfonating reaction, strengthen course of reaction, obtain
To secondary sulfonation mixture.
During secondary sulfonating reaction, produced heat is taken away by described second spiral coil 16, to described sulfonation
Mixture reducing temperature twice, controls the temperature of described sulfonated bodiess to be 30～60 DEG C.Specifically, described second spiral coil 16 is bag
Include：Ground floor endless solenoid, described ground floor endless solenoid is arranged on the side of described packed bed 15；Second layer annular spiral shell
Coil, described second layer endless solenoid is arranged in described packed bed 15, and ground floor endless solenoid and second layer annular
Serpentine pipe is spiraled by a pipe and forms.Recirculated cooling water is injected by described second spiral coil by described 3rd water inlet 22
In 16；Described second spiral coil 16 be cooling water flow out of by described by described 3rd outlet 23, anti-to described secondary sulfonation
Process is answered to be lowered the temperature.
After secondary sulfonating reaction terminates, sulfonated bodiess are pooled to the bottom of reactor 25, enter described neutralization through discharging opening
In tank 17, described sulfonated bodiess carry out aging, neutralization reaction in described neutralizing tank 17, obtain mahogany acid product salt.
Here, described device also includes：Hollow axle 27；Wherein, described hollow axle 27 and the side of described packed bed 15 connect
Connect, for driving described packed bed 15 to rotate by belt pulley 28, so that described sulfonated bodiess is sufficiently mixed with filling filler, carry out two
Secondary sulfonating reaction.
Described 3rd water inlet 22, described 3rd outlet 23 are each passed through described hollow axle 27, described second helical disk
Pipe 16 does not rotate with described hollow axle 27.
The sulfonation reaction device that the present embodiment provides has advantages below：
(1) good heat dissipation effect；Described sulfonation reaction device is cooled so that in product using two-stage radiation system
Portion's uniformity of temperature profile, it is to avoid because the by-product (or acid sludge) that localized hyperthermia causes produces.Additionally, utilizing the first helical disk
Pipe 14 and the second spiral coil 16 are radiated, and radiating contact area is big, and its radiating effect greatly improves, and decreases sulfonation process
The generation of by-product in the case of temperature is higher.
(2) interfacial tension of the mahogany acid product salt obtaining is lower, and quality is good.Sulfan and raw oil all with
Droplet or the contact sulfonation of mist form membrane, and continue on packed bed 15 strengthening reaction, it is to avoid raw material back-mixing, improve sulfonation
Efficiency；Obtained petroleum sulfonate product quality is more preferable.
(3) it is not required to add organic solvent in sulfonating reaction production process, it is to avoid pollution is to environment.
Embodiment three
During practical application, when carrying out process for sulfonation using the xanthator that the present invention provides, can obtain in the following manner
Take mahogany acid product salt；Wherein,
Experimental raw includes：Canned liquid sulphur trioxide, raw oil and ammonia；
The density of described liquid sulphur trioxide is：1.9g/cm3；Described raw oil is furfural extract oil, and described raw oil is close
Degree：0.955g/cm3, viscosity：15mPa S, arene content 40%；Ammonia is chemically pure reagent；
In addition, the aqueous phase that test interface tension force adopts is tap water, oil phase is dehydration degassing raw oil.
Before starting experiment, if ambient temperature is less than 30 DEG C, open the muff around reactor, set thermostatical circulating water
Temperature is 30 DEG C.Described thermostatical circulating water makes temperature of reaction kettle constant at 30 DEG C.
Open the first inlet and the second inlet respectively, control raw material oil flow rate is 75mL/min, sulfan
Flow velocity is 5mL/min；RPB motor speed is in 1000r/min.First spiral coil and the second spiral coil interior circulation
The temperature of condensed water is all set as 30 DEG C.
Arranging sulfonated products reaction condition in neutralizing tank is：First stand aging 24h, add in 40% ammonia spirit
With, and stir, settle 6h, be finally separating to obtain petroleum sulfonate crude product.Under above-mentioned same experimental conditions, adopt respectively
With autoclave sulfonation, common hypergravity liquid-liquid sulfonation and the present invention come synthetic petroleum sulfonate.To the 3 kinds of mahogany acids obtaining
Salt crude product has carried out the test such as acid sludge amount, unsulfonated oil, yield, interfacial tension, and experimental result is shown in Table 1.
Table 1 petroleum sulfonate crude product test result
| Test event | Autoclave sulfonation | Common hypergravity sulfonation | The present invention |
| Unsulfonated oil content, % | 15 | 12 | 10 |
| Acid sludge amount, % | 13 | 8 | 0 |
| Yield, % | 58 | 68 | 70 |
| Interfacial tension, mN m-1 | 4.2×10-2 | 1.5×10-2 | 2×10-3 |
As it can be seen from table 1 autoclave sulfonation byproduct at most, unsulfonated oil content highest.And adopt the present invention to provide
The petroleum sulfonate product quality that xanthator obtains all is better than common hypergravity process for sulfonation product.Here, described acid sludge amount
Size reflects the effect of the degree of coking and radiating in sulfonation process.
Example IV
During practical application, when the present embodiment carries out process for sulfonation using the xanthator that the present invention provides, can also pass through
In the following manner obtains mahogany acid product salt；Wherein,
Experimental raw includes：Liquid sulphur trioxide, raw oil, ammonia；Wherein；
The density of described liquid sulphur trioxide is：1.9g/cm3；Described raw oil is middle victory second line of distillation oil, described raw oil
Density：0.82g/cm3, viscosity：50mPa S, arene content：25%；Ammonia is chemically pure reagent；
In addition, the aqueous phase that test interface tension force adopts is tap water, oil phase is dehydration degassing raw oil.
Before starting experiment, if ambient temperature is less than 30 DEG C, open the muff around reactor, set thermostatical circulating water
Temperature is 30 DEG C.The heat release of described thermostatical circulating water makes kettle temperature rise.
Open the first inlet and the second inlet respectively, control raw material oil flow rate is 120mL/min, sulfan
Flow velocity is 4mL/min；RPB motor speed is in 1000r/min.First spiral coil and the second spiral coil interior circulation
The temperature of condensed water is all set as 30 DEG C.
Arranging sulfonated products reaction condition in neutralizing tank is：First stand aging 24h, add in 40% ammonia spirit
With, and stir, settle 6h, be finally separating to obtain petroleum sulfonate crude product.Under above-mentioned same experimental conditions, adopt respectively
The sulfonation reaction device being provided with autoclave sulfonation, common hypergravity liquid-liquid sulfonation and the present invention is come synthetic petroleum sulfonate.Right
3 kinds of obtained petroleum sulfonate crude products have carried out the test such as acid sludge amount, unsulfonated oil, yield, interfacial tension, experimental result
It is shown in Table 2.
Table 2 petroleum sulfonate crude product test result
| Test event | Autoclave sulfonation | Common hypergravity sulfonation | The present invention |
| Unsulfonated oil content, % | 47 | 30 | 24 |
| Acid sludge amount, % | 20 | 12 | 5 |
| Yield, % | 30 | 50 | 65 |
| Interfacial tension, mN m-1 | 8×10-1 | 3.0×10-2 | 9.5×10-3 |
From table 2 it can be seen that autoclave sulfonation byproduct at most, unsulfonated oil content highest.And adopt the present invention to provide
The petroleum sulfonate product quality that xanthator obtains all is better than common hypergravity process for sulfonation product.Here, described acid sludge amount
Size reflects the effect of the degree of coking and radiating in sulfonation process.
Embodiment five：
During practical application, when the present embodiment carries out process for sulfonation using the xanthator that the present invention provides, can by with
Under type obtains mahogany acid product salt；Wherein,
Experimental raw：Canned liquid sulphur trioxide, raw oil and ammonia；
The density of described liquid sulphur trioxide is：1.9g/cm3；Described raw oil is the wooden distillate of sheep three, described raw oil
Density：0.925g/cm3, viscosity：80mPa S, arene content：30%；Described ammonia is chemically pure reagent；
In addition, the aqueous phase that test interface tension force adopts is tap water, oil phase is dehydrated degassing raw oil for well.
Before starting experiment, if ambient temperature is less than 30 DEG C, open the muff around reactor, set thermostatical circulating water
Temperature is 30 DEG C.The heat release of described thermostatical circulating water makes kettle temperature degree rise.
Open the first inlet and the second inlet respectively, control raw material oil flow rate is 200mL/min, sulfan
Flow velocity is 10mL/min；RPB motor speed is in 1000r/min.First spiral coil and the second spiral coil interior circulation
The temperature of condensed water is all set as 30 DEG C.
Arranging sulfonated products reaction condition in neutralizing tank is：First stand aging 24h, add in 40% ammonia spirit
With, and stir, settle 6h, be finally separating to obtain petroleum sulfonate crude product.Under above-mentioned same experimental conditions, adopt respectively
With autoclave sulfonation, common hypergravity liquid-liquid sulfonation and apparatus of the present invention come synthetic petroleum sulfonate.To 3 kinds of obtained stones
Oily sulfonate crude product has carried out the test such as acid sludge amount, unsulfonated oil, yield, interfacial tension, and experimental result is shown in Table 3.
Table 3 petroleum sulfonate crude product test result
| Test event | Autoclave sulfonation | Common hypergravity sulfonation | The present invention |
| Unsulfonated oil content, % | 20 | 15 | 13 |
| Acid sludge amount, % | 10 | 5 | 0 |
| Yield, % | 55 | 68 | 72 |
| Interfacial tension, mN m-1 | 8.2×10-2 | 1.0×10-2 | 3.2×10-3 |
From table 3 it can be seen that autoclave sulfonation byproduct at most, unsulfonated oil content highest.And adopt the present invention to provide
The petroleum sulfonate product quality that xanthator obtains all is better than common hypergravity process for sulfonation product.Here, described acid sludge amount
Size reflects the effect of the degree of coking and radiating in sulfonation process.
The interfacial tension of the mahogany acid product salt obtained by the sulfonation reaction device that the present invention provides is low.Opened by interface
Power test finds：Interfacial tension between the petroleum sulfonate being synthesized its solution and raw oil is 10-3mN·m-1Quantity
Level, disclosure satisfy that tertiary oil recovery chemical flooding surfactant properties requirement.
The above, only presently preferred embodiments of the present invention, be not intended to limit protection scope of the present invention, all
Any modification, equivalent and improvement of being made within the spirit and principles in the present invention etc., should be included in the protection of the present invention
Within the scope of.
Claims (7)
1. a kind of sulfonating reaction method is it is characterised in that methods described includes：
Injection thermostatical circulating water, the temperature in reactor is maintained at 27-60 DEG C, stablizes the state of liquid sulphur trioxide；
Uniformly spray raw oil using gondola water faucet, uniformly spray described liquid sulphur trioxide using jet pipe, control described raw oil
The ratio of the first flow velocity and the second flow speed of described liquid sulphur trioxide is 15:1～30:1, make described raw oil and described liquid three
Sulfur oxide forms mist film overlapping region, a sulfonating reaction occurs, obtains a sulfonation mixture；
After a described sulfonation mixture reaches the first spiral coil, by injecting cooling water in the first spiral coil, right
A described sulfonation mixture is once lowered the temperature, and controls the temperature of a sulfonation mixture to be 30～60 DEG C；
After a described sulfonation mixture leaves described first spiral coil, when reaching packed bed, will be described using packed bed
One time sulfonation mixture is mixed with filling filler, carries out secondary sulfonating reaction, obtains secondary sulfonation mixture；
By injecting cooling water in the second spiral coil, to described secondary sulfonation mixture reducing temperature twice, control described secondary
The temperature of sulfonation mixture is 30～60 DEG C；Described second spiral coil is fixed in described packed bed；
After secondary sulfonating reaction terminates, sulfonated bodiess are pooled to the bottom of reactor, enter in neutralizing tank through discharging opening, in utilizing
With tank, secondary sulfonated bodiess are carried out with aging, neutralization reaction, obtain mahogany acid product salt.
2. a kind of sulfonation reaction device is it is characterised in that described device includes：
Muff, described muff is used for, by injecting thermostatical circulating water, the temperature in reactor being maintained at 27-60 DEG C, surely
Determine the state of liquid sulphur trioxide；
Gondola water faucet, described gondola water faucet is used for uniform ejection raw oil；
Jet pipe, described jet pipe is used for uniformly spraying described liquid sulphur trioxide, by controlling the first flow velocity of described raw oil
With the ratio of the second flow speed of described liquid sulphur trioxide 15:1～30:1, make described raw oil and described liquid sulphur trioxide shape
, there is a sulfonating reaction, obtain a sulfonation mixture in mist formation film overlapping region；
First spiral coil, when a described sulfonation mixture reaches described first spiral coil, described first spiral coil is used
In once lowering the temperature to a described sulfonation mixture, the temperature of described sulfonated bodiess is controlled to be 30～60 DEG C；
Packed bed, after a described sulfonation mixture leaves described first spiral coil, when reaching described packed bed, described fills out
Fill bed to mix a described sulfonation mixture with filling filler by rotation, carry out secondary sulfonating reaction, obtain secondary sulfonation
Mixture；
Second spiral coil, described second spiral coil is used for, to described secondary sulfonation mixture reducing temperature twice, controlling described sulphur
The temperature of compound is 30～60 DEG C；Described second spiral coil is fixed in described packed bed；
Neutralizing tank, after secondary sulfonating reaction terminates, sulfonated bodiess are pooled to the bottom of reactor, are neutralized tank through discharging opening
In, described neutralizing tank is used for carrying out aging, neutralization reaction to secondary sulfonated bodiess, obtains mahogany acid product salt.
3. right wants the device as described in 2 it is characterised in that described device also includes：
First water inlet, described first water inlet is used for injecting described thermostatical circulating water in described muff；
First outlet, described first outlet is used for for described thermostatical circulating water flowing out described muff.
4. device as claimed in claim 2 is it is characterised in that described device also includes：
First inlet, described first inlet is used for injecting described raw oil in described gondola water faucet.
5. device as claimed in claim 2 is it is characterised in that described device also includes：
Second water inlet, described second water inlet is used for injecting cooling water in described first spiral coil；
Second outlet, described second outlet is used for cooling water flow out of described first spiral coil by described.
6. device as claimed in claim 2 is it is characterised in that described device also includes：
3rd water inlet, described 3rd water inlet is used for injecting cooling water in described second spiral coil；
3rd outlet, described 3rd outlet is used for cooling water flow out of described second spiral coil by described.
7. device as claimed in claim 2 is it is characterised in that described second spiral coil includes：
Ground floor endless solenoid, described ground floor endless solenoid is arranged on the side of described packed bed；
Second layer endless solenoid, described second layer endless solenoid is arranged in described packed bed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410797837.3A CN104557622B (en) | 2014-12-18 | 2014-12-18 | Sulfonation reaction method and device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410797837.3A CN104557622B (en) | 2014-12-18 | 2014-12-18 | Sulfonation reaction method and device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104557622A CN104557622A (en) | 2015-04-29 |
| CN104557622B true CN104557622B (en) | 2017-02-08 |
Family
ID=53074801
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410797837.3A Active CN104557622B (en) | 2014-12-18 | 2014-12-18 | Sulfonation reaction method and device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104557622B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109876758A (en) * | 2019-04-02 | 2019-06-14 | 天津市科德化工有限公司 | Sulpho Tobias Acid sulfonating reaction kettle |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3213131A (en) * | 1961-07-17 | 1965-10-19 | Phillips Petroleum Co | Filtration of petroleum sulfonate product |
| CA1227493A (en) * | 1983-11-23 | 1987-09-29 | Wayne E. Luetzelschwab | Process for the production of petroleum sulfonate |
| CN1053174C (en) * | 1996-07-12 | 2000-06-07 | 天津大学 | Method for sulfonating liquid state organics by gas phase sulfur trioxide and its equipment |
| CN1923352A (en) * | 2005-09-01 | 2007-03-07 | 中国石油天然气股份有限公司 | Spray mist film sulphonation reactor |
| CN102527299A (en) * | 2010-12-17 | 2012-07-04 | 中国石油天然气股份有限公司 | Sulfonation reaction device and application thereof |
| CN103130690B (en) * | 2011-12-02 | 2014-09-17 | 中国科学院大连化学物理研究所 | Method of producing petroleum sulfonate by micro reaction system grading sulfonation |
| CN203159511U (en) * | 2013-04-04 | 2013-08-28 | 胜利油田中胜环保有限公司 | Petroleum sulfonate production device |
-
2014
- 2014-12-18 CN CN201410797837.3A patent/CN104557622B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104557622A (en) | 2015-04-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN203612955U (en) | Liquid sulfur degassing device | |
| CN106943978B (en) | A kind of reactor suitable for high viscosity fast reaction system | |
| CN103288642A (en) | Method for preparing vegetable oil polyalcohol by continuous process | |
| BRPI0611709A2 (en) | method and apparatus for fluid-liquid reactions | |
| CN109400867A (en) | A kind of reaction system preparing polyether polyol and method | |
| CN104907008B (en) | A kind of toluene direct oxidation prepares the reaction unit and method of benzoic acid and benzaldehyde | |
| TW201204825A (en) | A method for removing sulfides from a liquid fossil fuel and the device using the same | |
| CN108579639B (en) | Device and method for preparing oxo-isophorone | |
| CN104557622B (en) | Sulfonation reaction method and device | |
| WO2017080115A1 (en) | Vegetable oil polyol and preparation method therefor and use thereof | |
| CN101318112B (en) | Method for preparing anionic surface active agent for displacement of reservoir oil | |
| US20210179520A1 (en) | Synthesis method for highly selective 2-methylallyl chloride and synthesis reactor thereof | |
| CN203790949U (en) | Methyl capped polyether production device | |
| CN105251433A (en) | Liquid acid alkylation reactor and application method thereof | |
| CN105937387A (en) | Thickened oil foam oil drive system | |
| CN105268394A (en) | Liquid acid alkylation reactor and application method thereof | |
| CN102796030A (en) | Method and device for preparing 3-methylmercapto-propionaldehyde through liquid-liquid reaction of methyl mercaptan and acraldehyde | |
| CN105801860A (en) | Tower-type continuous production technology of polymethyl triethoxy silane | |
| CN104370789A (en) | Method for preparing peroxidized dicarbonate (2-ethylhexyl) ester (EHP) by continuous flow | |
| CN104556281B (en) | A kind of method removing the carbon dioxide contained in water | |
| CN102127017B (en) | Method for fast producing caprolactam by means of strengthening and mixing | |
| CN101508633A (en) | Process and apparatus for preparing methanal with low transformational cycle method | |
| CN106966930B (en) | A kind of method of supergravity reactor Green synthesis petroleum sulfonate for tertiary oil recovery | |
| CN105170040B (en) | A kind of reaction dress device for producing ozone carburetion | |
| CN106977393B (en) | The technique of continuous production calcium naphthenate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |