CN107200698A - A kind of method for removing sulfonating reaction heat - Google Patents
A kind of method for removing sulfonating reaction heat Download PDFInfo
- Publication number
- CN107200698A CN107200698A CN201610148551.1A CN201610148551A CN107200698A CN 107200698 A CN107200698 A CN 107200698A CN 201610148551 A CN201610148551 A CN 201610148551A CN 107200698 A CN107200698 A CN 107200698A
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- CN
- China
- Prior art keywords
- solvent
- reaction heat
- sulfonating
- mixer
- feedstock oil
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
- C07C303/44—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/62—Sulfonated fats, oils or waxes of undetermined constitution
Abstract
The present invention provides a kind of method for removing sulfonating reaction heat.Its technical scheme is：Feedstock oil and sulfur trioxide are diluted using easy evaporation solvent, Hi-mixer is then entered in proportion（2）, reactive evaporation device is rapidly entered after mixing（4）, solvent rapid vaporization removes reaction heat, and the solvent of evaporation collects through supercooling, returns to Hi-mixer（2）The feed end of feedstock oil or sulfonating agent, is diluted to raw material again, reactive evaporation device（4）Interior sulfonated products are by neutralizing, dehydration, after desolventizing, as mahogany acid product salt.The present invention realizes the fast transfer of sulfonating reaction heat inside material, maintains reaction temperature stable in course of reaction, and material is well mixed, and solvent load is few, and production efficiency is high, and apparatus and process is simple, is easy to continuous production.
Description
Technical field：
The present invention relates to sulfonating reaction technical field, especially a kind of method for removing sulfonating reaction heat.
Background technology：
In the production process for carrying out petroleum sulfonate, feed stock conversion is low and sulfonation phenomenon excessively is the outstanding problem faced.It is main
It is that sulfonating reaction can be completed instantaneously to want reason, and produces a large amount of reaction heat.Enter in the feedstock oil of complicated components with sulfur trioxide
During row sulfonating reaction, because the reaction activity of different component is different, make feedstock oil conversion uneven, and cause amount of localized heat fast
Speed increases and promotes the continuation reaction of partly sulfonation material, prevents feedstock oil with sulfonating agent from being reacted by equivalent.Therefore, state
A variety of raising feedstock oils and the research of sulfonating agent efficiency are inside had been carried out, such as CN101318112A, which has been reported, uses hypergravity
The method of 200 ~ 550 DEG C of distillates of technology sulfonation, improves material transfer velocity and engagement capacity, but does not illustrate to move heat side
Method；The method that CN1275431A has reported 320 ~ 380 DEG C of fraction oil of petroleum of membrane-type sulfonation, although membrane-type sulfonation reaction has stronger
Material contact and reaction heat-exchange capacity, but for composition is complicated and sulfonating reaction of sticky material, it is easy to produce sulfonation
Device clogging, and it is not suitable for the production of petroleum sulfonate；CN1472199A has reported cascade reaction tank and has continuously prepared oil sulphur
Although the method for hydrochlorate, feedstock oil conversion ratio is improved by reaction of high order, but there is material and mix uneven, heat transfer
Speed is slow, part crosses the problems such as sulfonation phenomenon is serious.
It is an object of the invention to overcome reaction heat branch problem present in above-mentioned petroleum sulfonate production process, solve
There is provided a kind of mahogany acid realized the equal qualitative response of material and remove reaction heat rapidly for contradiction between high mass transfer and flash heat transfer
Salt production method.On the basis of progress reaction mass homogenizes reaction, it can remove rapidly in course of reaction inside material
Reaction heat, it is ensured that material is uniformly carried out at rational temperature, improves materials conversion rate and avoids hot-spot from showing with sulfonation is crossed
The generation of elephant.
The content of the invention
There is provided practical, sensitive, efficient, standard reasonable in design aiming at the defect that prior art is present for the purpose of the present invention
A kind of method of true removal sulfonating reaction heat.Its technical scheme is：Feedstock oil and sulfur trioxide are entered using easy evaporation solvent
Row dilution, then enters Hi-mixer in proportion, and reactive evaporation device is rapidly entered after mixing, and solvent rapid vaporization removes reaction
Heat, the solvent of evaporation is collected through supercooling, returns to the feed end of Hi-mixer feedstock oil or sulfonating agent, and raw material is carried out again
Dilution, sulfonated products in reactive evaporation device are by neutralizing, dehydration, after desolventizing, as mahogany acid product salt.
Feedstock oil holding vessel Road pipeline connection Hi-mixer, the branch line of feedstock oil holding vessel Road is through measuring pump
Connect surge tank, Hi-mixer overhead line connection sulfonating agent holding vessel, Road pipeline coupled reaction evaporator, reactive evaporation
Device overhead line connects surge tank through cooler, and lower pipelines are exported provided with sulfonated products, and surge tank overhead line is provided with
Vavuum pump.
Easy evaporation solvent is：In dichloromethane, dichloroethanes, chloroform, difluoro tetrachloroethanes, trifluorotrichloroethane
It is one or more of.
Hi-mixer is：One kind in pipe-line mixer, homogenizer, supergravity reactor, injection reactor.
Feedstock oil is：One kind in crude oil fractions oil, furfural extract oil, high aromatic oil.
The present invention has following features compared with prior art：
1st, the fast transfer of sulfonating reaction heat inside material is realized.Because traditional sulfonation reactor uses wall-type heat exchange, pass
Matter speed is faster, and the removal of heat is more difficult；Material is more sticky, and heat exchange efficiency is lower.In the technical program, material is run through
Blender enters in low-pressure reactor, the low-pressure state of reactor and the reaction heat of release, promotes rapid solvent evaporation, makes anti-
Hot it should be transported rapidly with solvent evaporation.Because reaction heat is taken away by the solvent evaporation in reactant mixture material, and it is traditional
Cooling water heat exchanger indirect type takes heat to have essential distinction, overcomes the lance that mass transfer velocity and flash heat transfer are improved in sulfonating reaction
Shield, solves the branch problem of sticky material internal heat.
2nd, reaction temperature stable in course of reaction is maintained.Because the present invention is made by adjusting reactor internal pressure
Solvent is rapidly reached gasification shape body, heat is taken away by vaporized solvent, as long as keeping in the stable pressure of inside reactor, material
Portion's temperature can just keep constant, thus, it effectively prevent hot-spot phenomenon.
3rd, material is well mixed.Reaction mass is first by entering reactor after high speed strong stirring, material is fully mixed
Close, be conducive to the equal qualitative response of storeroom.
4th, solvent load is few, and production efficiency is high.The solvent of evaporation returns to material input after collecting, to reaction mass again
It is diluted, solvent is recycled in closed system, solvent in the dilution ratio and product of reaction mass can be reduced
Content, so as to reduce the workload to removing solvent bank in raw material dilution and product, improves production efficiency.
5th, apparatus and process is simple, is easy to continuous production.There is no the production equipment of complexity in system, technique is simple, be easy to
Operation.After production reaches stable state, material continuously enters reaction system, and sulfonated products are continuously removed, and realizes continuous
Change production process.
Brief description of the drawings
Fig. 1 is process units structural representation of the present invention.
Embodiment
As shown in figure 1, feedstock oil is diluted into the solution that mass percent is 20% ~ 80% with solvent deposits in feedstock oil storage
Deposit in tank 1, with solvent by SO3It is diluted to the solution that mass percent is 10% ~ 40% to deposit in sulfonating agent holding vessel 3, raw material
Oil is diluted with sulfonating agent using homogeneous solvent.Adjustment flow makes sulfonating agent compare 1 by solution quality with feedstock oil:0.5 ~ 2 point
Not Jin Ru Hi-mixer 2, reactive evaporation device 4 is quickly entered after mixing, vavuum pump 6 effect under, in reactive evaporation device 4
Pressure controllable is made as 0.001 ~ 0.2MPa, because the solvent in the action-reaction evaporator 4 of reaction heat is rapidly reached boiling point, evaporation
Solvent cooled by 0 ~ -20 DEG C of coolers 5 after be collected in surge tank 8, then by measuring pump 9 again by the molten of collection
Agent is returned into the output channel of feedstock oil holding vessel 1 or returned into the output channel of sulfonating agent holding vessel 3, and solvent can also be made to enter simultaneously
Above two material output channel, solvent is recycled in system, and raw material is diluted again.Keep in surge tank 8
The quality that solvent is collected enters the quality and sulphur of Hi-mixer 2 with the identical in quality of the discharge of measuring pump 9, feedstock oil and sulfonating agent
Change the identical in quality of the discharge sulfonated products of product exit 7, material reaches poised state, can keep continuous production.Sulfonation is produced
Thing is neutralized, is dehydrated, can obtain mahogany acid product salt after desolventizing.
Embodiment 1
1）Use CH2Cl2260 ~ 530 DEG C of distillates are diluted to 50%（Mass percent）Concentration deposit in feedstock oil storage
In tank 1.Use CH2Cl2By sulfonating agent S03It is formulated as 30%（Mass percent）Solution deposit in sulfonating agent holding vessel 3.
2）Feedstock oil flow 1.80Kg/h, sulfonation agent flux 1.35Kg/h are controlled, it is mixed in 1500r/min into homogenizer
Close.
3）The pre-stored CH of surge tank 82Cl25Kg, the control flow 0.945Kg/h of measuring pump 9, returns and goes out into sulfonating agent holding vessel 3
In expects pipe line.
4）0.09 ~ the 0.11MPa of pressure of reactive evaporation device 4,35 ~ 45 DEG C of temperature.
5）Cooler 5 is passed through -10 ~ 0 DEG C of freezing liquid to solvent lowered temperature reclamation.
6）Sulfonated products use 25%（Mass percent）Ammoniacal liquor is neutralized, neutralization activity thing content 17.1%.
7）It is dehydrated active matter content 48.2% after desolventizing.
8）Single sulfonic acid content 73.8%, disulfonic acid content 24.1%, polysulfonate content 2.1% in active matter.
Embodiment 2
1）Use CH2Cl2260 ~ 530 DEG C of distillates are diluted to 50%（Mass percent）Concentration deposit in feedstock oil storage
In tank 1.Use CH2Cl2By sulfonating agent S03It is formulated as 30%（Mass percent）Solution deposit in sulfonating agent holding vessel 2.
2）Feedstock oil flow 1.80Kg/h, sulfonation agent flux 1.26Kg/h are controlled, it is mixed in 1500r/min into homogenizer
Close.
3）The pre-stored CH of surge tank 82Cl25Kg, the control flow 0.9Kg/h of measuring pump 9, returns and is discharged into feedstock oil holding vessel 1
In pipeline, return in the discharging pipeline of sulfonating agent holding vessel 3.
4）0.03 ~ the 0.05MPa of pressure of reactive evaporation device 4,20 ~ 35 DEG C of temperature.
5）Cooler 5 is passed through -10 ~ 0 DEG C of freezing liquid to solvent lowered temperature reclamation.
6）Sulfonated products use 25%（Mass percent）Ammoniacal liquor is neutralized, neutralization activity thing content 16.7%.
7）It is dehydrated active matter content 46.8% after desolventizing.
8）Single sulfonic acid content 75.3%, disulfonic acid content 24.5%, polysulfonate content 1.2% in active matter.
Embodiment 3
1）Use C2H4Cl2260 ~ 530 DEG C of distillates are diluted to 50%（Mass percent）Concentration deposit in feedstock oil storage
In tank 1.Use C2H4Cl2By sulfonating agent S03It is formulated as 30%（Mass percent）Solution deposit in sulfonating agent holding vessel 2.
2）Feedstock oil flow 1.8Kg/h, sulfonation agent flux 1.17Kg/h are controlled, is mixed into homogenizer in 1500r/min.
3）The pre-stored C of surge tank 82H4Cl25Kg, the control flow 0.82Kg/h of measuring pump 9, returns and goes out into sulfonating agent holding vessel 3
In expects pipe line.
4）0.05 ~ the 0.07MPa of pressure of reactive evaporation device 4,50 ~ 70 DEG C of temperature.
5）Cooler 5 is passed through -10 ~ 0 DEG C of freezing liquid to solvent lowered temperature reclamation.
6）Sulfonated products use 25%（Mass percent）Ammoniacal liquor is neutralized, neutralization activity thing content 16.1%.
7）It is dehydrated active matter content 45.7% after desolventizing.
8）Single sulfonic acid content 71.9%, disulfonic acid content 24.2%, polysulfonate content 3.9% in active matter.
Claims (5)
1. a kind of method for removing sulfonating reaction heat, it is characterised in that：Feedstock oil and sulfur trioxide are entered using easy evaporation solvent
Row dilution, then enters Hi-mixer in proportion（2）, reactive evaporation device is rapidly entered after mixing（4）, the shifting of solvent rapid vaporization
Except reaction heat, the solvent of evaporation is collected through supercooling, returns to Hi-mixer（2）The feed end of feedstock oil or sulfonating agent, again
Raw material is diluted, reactive evaporation device（4）Interior sulfonated products are by neutralizing, dehydration, after desolventizing, as petroleum sulfonate
Product.
2. a kind of method for removing sulfonating reaction heat according to claim 1, it is characterised in that：Feedstock oil holding vessel（1）
Road pipeline connection Hi-mixer（2）, feedstock oil holding vessel（1）The branch line of Road is through measuring pump（9）Connect surge tank
（8）, Hi-mixer（2）Overhead line connects sulfonating agent holding vessel（3）, Road pipeline coupled reaction evaporator（4）, reaction steaming
Send out device（4）Overhead line is through cooler（5）Connect surge tank（8）, lower pipelines are provided with sulfonated products outlet（7）, surge tank
（8）Overhead line is provided with vavuum pump（6）.
3. a kind of method for removing sulfonating reaction heat according to claim 1 or 2, it is characterised in that：It is described easily to evaporate molten
Agent is：One or more in dichloromethane, dichloroethanes, chloroform, difluoro tetrachloroethanes, trifluorotrichloroethane.
4. a kind of method for removing sulfonating reaction heat according to claim 1 or 2, it is characterised in that：The efficient mixing
Device（2）For：One kind in pipe-line mixer, homogenizer, supergravity reactor, injection reactor.
5. a kind of method for removing sulfonating reaction heat according to claim 1 or 2, it is characterised in that：The feedstock oil is：
One kind in crude oil fractions oil, furfural extract oil, high aromatic oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610148551.1A CN107200698A (en) | 2016-03-16 | 2016-03-16 | A kind of method for removing sulfonating reaction heat |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610148551.1A CN107200698A (en) | 2016-03-16 | 2016-03-16 | A kind of method for removing sulfonating reaction heat |
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| Publication Number | Publication Date |
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| CN107200698A true CN107200698A (en) | 2017-09-26 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201610148551.1A Pending CN107200698A (en) | 2016-03-16 | 2016-03-16 | A kind of method for removing sulfonating reaction heat |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115594616A (en) * | 2022-10-09 | 2023-01-13 | 浙江迪邦化工有限公司（Cn） | Multistage continuous sulfonation method of 1-aminoanthraquinone |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101318112A (en) * | 2008-07-18 | 2008-12-10 | 北京化工大学 | Method for preparing anionic surface active agent for displacement of reservoir oil |
| CN102127017A (en) * | 2011-01-13 | 2011-07-20 | 湘潭大学 | Method for fast producing caprolactam by means of strengthening and mixing |
| CN102295586A (en) * | 2010-06-23 | 2011-12-28 | 中国科学院大连化学物理研究所 | Method for synthesizing petroleum sulfonate in micro reactors |
| CN103130690A (en) * | 2011-12-02 | 2013-06-05 | 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 |
-
2016
- 2016-03-16 CN CN201610148551.1A patent/CN107200698A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101318112A (en) * | 2008-07-18 | 2008-12-10 | 北京化工大学 | Method for preparing anionic surface active agent for displacement of reservoir oil |
| CN102295586A (en) * | 2010-06-23 | 2011-12-28 | 中国科学院大连化学物理研究所 | Method for synthesizing petroleum sulfonate in micro reactors |
| CN102127017A (en) * | 2011-01-13 | 2011-07-20 | 湘潭大学 | Method for fast producing caprolactam by means of strengthening and mixing |
| CN103130690A (en) * | 2011-12-02 | 2013-06-05 | 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115594616A (en) * | 2022-10-09 | 2023-01-13 | 浙江迪邦化工有限公司（Cn） | Multistage continuous sulfonation method of 1-aminoanthraquinone |
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Application publication date: 20170926 |