CN111470928A - Method for producing long-chain alkylbenzene by using hydrogen fluoride - Google Patents
Method for producing long-chain alkylbenzene by using hydrogen fluoride Download PDFInfo
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- CN111470928A CN111470928A CN202010294860.6A CN202010294860A CN111470928A CN 111470928 A CN111470928 A CN 111470928A CN 202010294860 A CN202010294860 A CN 202010294860A CN 111470928 A CN111470928 A CN 111470928A
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- Prior art keywords
- hydrogen fluoride
- producing long
- alkylbenzene
- olefin
- chain
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910000040 hydrogen fluoride Inorganic materials 0.000 title claims abstract description 53
- 150000004996 alkyl benzenes Chemical class 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 16
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 14
- 150000001336 alkenes Chemical class 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000010924 continuous production Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000010923 batch production Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 208000012839 conversion disease Diseases 0.000 abstract description 2
- 238000007867 post-reaction treatment Methods 0.000 abstract description 2
- 239000002253 acid Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000003599 detergent Substances 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 230000029936 alkylation Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- -1 alkylbenzene sulfonate Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
- C07C2/66—Catalytic processes
- C07C2/70—Catalytic processes with acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/12—Fluorides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/08—Halides
- C07C2527/12—Fluorides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/08—Halides
- C07C2527/12—Fluorides
- C07C2527/1206—Hydrogen fluoride
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method for producing long-chain alkylbenzene by using hydrogen fluoride, which comprises the following steps: c is to be14‑24Olefin and benzene are mixed, hydrogen fluoride is added, alkylation reaction is carried out, and then layering, stripping and resolving are carried out, thus obtaining C14‑24An alkylbenzene; the invention provides a method for producing long-chain alkylbenzene by using hydrogen fluoride, which adopts a hydrogen fluoride alkylation process to produce the long-chain alkylbenzene, has high reaction conversion rate, recycles a catalyst, is clean and efficient, and has product quality superior to that of other process products; the reaction yield is high, the yield is more than 99%, the reaction selectivity is good, the byproducts are few, the post-reaction treatment is simple, HF and benzene are easy to separate and remove, and the method has good economic and social benefits.
Description
Technical Field
The invention relates to a method for producing long-chain alkylbenzene by using hydrogen fluoride, belonging to the field of synthesis of long-chain alkylbenzene.
Background
The long-chain alkylbenzene is a main raw material of the long-chain alkylbenzene sulfonate detergent, the lubricating oil detergent is a very important component in vehicle oil and marine oil, and the lubricating oil detergent has the main function of enabling insoluble substances generated in the using process of the lubricating oil to be in a colloid suspension state, avoiding further forming carbon deposit, paint film or oil sludge, keeping the interior of an engine clean, ensuring more stable oil pressure, stronger power and more environment-friendly emission. For technical reasons, long-chain alkylbenzenes have long been imported. In recent years, several domestic manufacturers begin to adopt solid acid or ionic liquid technology to produce long-chain alkylbenzene, but the product quality is poor, the number of byproducts is large, and the long-chain alkylbenzene cannot replace imported products to be used in high-end markets. Meanwhile, a large amount of waste solid catalyst and acid liquor are generated, which does not meet the large trend of green and clean production, so that high-quality long-chain alkylbenzene is urgently needed at home and abroad.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for producing long-chain alkylbenzene by using hydrogen fluoride, which aims to solve the problems in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a process for producing long chain alkylbenzenes using hydrogen fluoride comprising the steps of: mixing olefin and benzene, adding hydrogen fluoride to carry out alkylation reaction, layering, stripping and resolving to obtain C14-24An alkylbenzene.
Further, the olefin is a single-carbon or multi-carbon olefin with 14-24 carbon atoms.
Further, the olefin is C14-24An olefin.
Further, the molar ratio of the benzene to the olefin is 1-20: 1.
Further, the volume ratio of the total volume of the olefin and the benzene to the volume of the hydrogen fluoride is 1: 0.5-5.
Furthermore, the temperature of the alkylation reaction is 30-75 ℃, and the reaction pressure is 0.4-1.3 Mpa.
Further, the above production method may be carried out by a batch-type or continuous production method.
The batch production mode comprises the following steps: stopping stirring after alkylation reaction for 10-60min, standing until materials are layered, separating upper layer materials, and distilling to obtain C14-24An alkylbenzene.
The steps of the continuous production mode are as follows: the material after the alkylation reaction is finishedLayering, separating the upper material, distilling to obtain C14-24An alkylbenzene.
The mass concentration of the hydrogen fluoride is more than or equal to 99.9 percent, and the hydrogen fluoride is liquid hydrogen fluoride.
The hydrogen fluoride adopted by the invention is liquid hydrogen fluoride, and the product is C14-24Alkylbenzene of formula CnH2n+1－C6H5Of the chemical formula
The average molecular weight is about 350-450, and the liquid is colorless and odorless water-white liquid.
The invention discloses a method for producing long-chain alkylbenzene by using hydrogen fluoride, which comprises the following synthetic process routes:
the invention is suitable for the production of single-carbon alkylbenzene or multi-carbon alkylbenzene with alkyl chain of 14-24 carbon atoms.
Compared with the prior art, the invention has the following beneficial effects because the technology is adopted:
the invention provides a method for producing long-chain alkylbenzene by using hydrogen fluoride, which adopts a hydrogen fluoride alkylation process to produce the long-chain alkylbenzene, has high reaction conversion rate, recycles a catalyst, is clean and efficient, and has product quality superior to that of other process products; the reaction yield is high, the yield is more than 99%, the reaction selectivity is good, the byproducts are few, the separation is not needed, the post-reaction treatment is simple, the HF and the benzene are easy to separate and remove, and the economic benefit and the social benefit are good.
Detailed Description
The present invention will be further illustrated with reference to the following specific embodiments.
Example 1: intermittent production process
A process for producing long chain alkylbenzenes using hydrogen fluoride comprising the steps of:
(1) adding 10kg of C14-24Olefin and 21kg benzene in a reaction vessel at 33 degrees C;
(2) adding 70kg of hydrogen fluoride into the mixture obtained in the step (1), stirring and uniformly mixing at 33 ℃ and 0.85Mpa, and carrying out alkylation reaction;
(3) stopping stirring after alkylation reaction for 30min (after temperature does not rise obviously), standing until materials are layered, separating materials on the upper layer, and distilling to remove unreacted benzene and a small amount of hydrogen fluoride to obtain C14-24An alkylbenzene.
The mass concentration of the hydrogen fluoride in the step (2) is more than or equal to 99.9 percent, and the hydrogen fluoride is liquid hydrogen fluoride.
Example 2: continuous production process
A process for producing long chain alkylbenzenes using hydrogen fluoride comprising the steps of:
(1) 50kg/h C14-24Olefin, 106kg/h benzene and 264kg/h hydrogen fluoride are fed into a mixer and mixed at 35 ℃ and 0.75 Mpa;
(2) feeding the mixed materials into an alkylation reactor, and carrying out alkylation reaction at 35 ℃ and 0.75 Mpa;
(3) introducing the product after the alkylation reaction into an acid delayer for layering;
(4) introducing the layered upper material into a fractionating tower for separation, and removing unreacted benzene and a small amount of hydrogen fluoride to obtain C14-24An alkylbenzene.
(5) The lower material hydrogen fluoride in the acid delayer can be recycled after regeneration.
The mass concentration of the hydrogen fluoride in the step (2) is more than or equal to 99.9 percent, and the hydrogen fluoride is liquid hydrogen fluoride.
Example 3: continuous production process
A process for producing long chain alkylbenzenes using hydrogen fluoride comprising the steps of:
(1) 300kg/h C20-24Olefin, 796kg/h benzene and 2460kg/h hydrogen fluoride were fed into a mixer and mixed at 40 ℃;
(2) feeding the mixed materials into an alkylation reactor, and carrying out alkylation reaction at 40 ℃ and 0.65 Mpa;
(3) introducing the product after the alkylation reaction into an acid delayer for layering;
(4) introducing the layered upper material into a fractionating tower for separation, and removing unreacted benzene and a small amount of hydrogen fluoride to obtain C20-24An alkylbenzene.
(5) The lower material hydrogen fluoride in the acid delayer can be recycled after regeneration.
The mass concentration of the hydrogen fluoride in the step (2) is more than or equal to 99.9 percent, and the hydrogen fluoride is liquid hydrogen fluoride.
Example 4: comparative examples
(1) 10kgC20-24Olefin and 31kg of benzene (the mol ratio of the benzene to the olefin is 12:1) are injected into an autoclave, and the temperature is raised to 80 ℃ while stirring;
(2) adding 0.08kg of ionic liquid catalyst (the mass ratio of ionic liquid to olefin is 0.008:1) into the mixture obtained in the step (1) after the temperature is constant, keeping the reaction temperature at 80 ℃ and the pressure at 0.4-1.3Mpa, and uniformly mixing;
(3) after reacting for 1-1.5h, stopping heating, cooling to 40 ℃ and discharging. Evaporating most excessive benzene at normal pressure, evaporating residual benzene at reduced pressure, settling for 12h, and separating residual catalyst to obtain C20-24An alkylbenzene.
The reaction conditions for examples 1-4 are shown in the following table:
the products produced in examples 1-4 were analyzed for higher alkyl benzenes and the results were as follows:
the above-mentioned embodiments are merely preferred embodiments of the present invention, and should not be construed as limiting the present invention, and the scope of the present invention should be defined by the claims, and equivalents including technical features of the claims, i.e., equivalent modifications within the scope of the present invention.
Claims (9)
1. A process for producing long chain alkylbenzenes using hydrogen fluoride comprising the steps of: mixing olefin and benzene, adding hydrogen fluoride to carry out alkylation reaction, layering, stripping and resolving to obtain C14-24An alkylbenzene.
2. The process for producing long-chain alkylbenzenes using hydrogen fluoride, as claimed in claim 1, wherein: the olefin is single-carbon or multi-carbon olefin with 14-24 carbon atoms.
3. The process for producing long-chain alkylbenzenes using hydrogen fluoride, as claimed in claim 1, wherein: the molar ratio of benzene to olefin is 1-20: 1.
4. The process for producing long-chain alkylbenzenes using hydrogen fluoride, as claimed in claim 1, wherein: the volume ratio of the total volume of the olefin and the benzene to the volume of the hydrogen fluoride is 1: 0.5-5.
5. The process for producing long-chain alkylbenzenes using hydrogen fluoride, as claimed in claim 1, wherein: the alkylation reaction temperature is 30-75 deg.C, and the reaction pressure is 0.4-1.3 Mpa.
6. A process for the production of long chain alkyl benzenes with hydrogen fluoride as set forth in claims 1 to 5, wherein: the production mode is carried out by adopting a batch type or continuous type production mode.
7. The process for producing long-chain alkylbenzenes using hydrogen fluoride, according to claim 6, wherein: the batch production mode comprises the following steps: stopping stirring after alkylation reaction for 10-60min, standing until materials are layered, separating upper layer materials, and distilling to obtain C14-24An alkylbenzene.
8. The process for producing long-chain alkylbenzenes using hydrogen fluoride, according to claim 6, wherein: the steps of the continuous production mode are as follows: layering the material after the alkylation reaction, separating the upper layer material, and distilling to obtain C14-24An alkylbenzene.
9. The process for producing long-chain alkylbenzenes using hydrogen fluoride, according to claim 6, wherein: the mass concentration of the hydrogen fluoride is more than or equal to 99.9 percent, and the hydrogen fluoride is liquid hydrogen fluoride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010294860.6A CN111470928A (en) | 2020-04-15 | 2020-04-15 | Method for producing long-chain alkylbenzene by using hydrogen fluoride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010294860.6A CN111470928A (en) | 2020-04-15 | 2020-04-15 | Method for producing long-chain alkylbenzene by using hydrogen fluoride |
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| Publication Number | Publication Date |
|---|---|
| CN111470928A true CN111470928A (en) | 2020-07-31 |
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| CN202010294860.6A Pending CN111470928A (en) | 2020-04-15 | 2020-04-15 | Method for producing long-chain alkylbenzene by using hydrogen fluoride |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5185485A (en) * | 1991-06-28 | 1993-02-09 | Monsanto Company | Process for preparing alkylbenzene |
| CN1460669A (en) * | 2003-04-15 | 2003-12-10 | 中国石化集团金陵石油化工有限责任公司 | Liquid hydrogen fluoride catalytic alkylation multistage reaction |
| CN101386782A (en) * | 2007-09-10 | 2009-03-18 | 中国石油天然气股份有限公司 | Alkylation synthesis of C14-C20Method for preparing alkylbenzene for oil displacement |
| CN108358741A (en) * | 2017-12-25 | 2018-08-03 | 中国石油集团东北炼化工程有限公司沈阳分公司 | Long chain olefin alkylation heavy alkyl benzene device |
| CN109516893A (en) * | 2018-11-16 | 2019-03-26 | 中国石油集团东北炼化工程有限公司沈阳分公司 | A kind of heavy-fluid wax dehydrogenation and re-request are alkylated heavy alkyl benzene technique processed |
-
2020
- 2020-04-15 CN CN202010294860.6A patent/CN111470928A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5185485A (en) * | 1991-06-28 | 1993-02-09 | Monsanto Company | Process for preparing alkylbenzene |
| CN1460669A (en) * | 2003-04-15 | 2003-12-10 | 中国石化集团金陵石油化工有限责任公司 | Liquid hydrogen fluoride catalytic alkylation multistage reaction |
| CN101386782A (en) * | 2007-09-10 | 2009-03-18 | 中国石油天然气股份有限公司 | Alkylation synthesis of C14-C20Method for preparing alkylbenzene for oil displacement |
| CN108358741A (en) * | 2017-12-25 | 2018-08-03 | 中国石油集团东北炼化工程有限公司沈阳分公司 | Long chain olefin alkylation heavy alkyl benzene device |
| CN109516893A (en) * | 2018-11-16 | 2019-03-26 | 中国石油集团东北炼化工程有限公司沈阳分公司 | A kind of heavy-fluid wax dehydrogenation and re-request are alkylated heavy alkyl benzene technique processed |
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Application publication date: 20200731 |