CN105130818A - Isooctyl nitrate continuous preparation method and reactor - Google Patents
Isooctyl nitrate continuous preparation method and reactor Download PDFInfo
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- CN105130818A CN105130818A CN201510152100.0A CN201510152100A CN105130818A CN 105130818 A CN105130818 A CN 105130818A CN 201510152100 A CN201510152100 A CN 201510152100A CN 105130818 A CN105130818 A CN 105130818A
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- reactor
- sulfuric acid
- isooctyl ester
- ester nitrate
- isooctyl
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- NNKQLUVBPJEUOR-UHFFFAOYSA-N 3-ethynylaniline Chemical compound NC1=CC=CC(C#C)=C1 NNKQLUVBPJEUOR-UHFFFAOYSA-N 0.000 title abstract 4
- 238000002360 preparation method Methods 0.000 title abstract 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 72
- 150000002148 esters Chemical class 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 36
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 19
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 17
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 229910002651 NO3 Inorganic materials 0.000 claims description 39
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 39
- -1 isooctyl Chemical group 0.000 claims description 39
- 238000010924 continuous production Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000012043 crude product Substances 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 6
- 239000003507 refrigerant Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 230000032050 esterification Effects 0.000 claims 1
- 238000005886 esterification reaction Methods 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 21
- 238000004519 manufacturing process Methods 0.000 abstract description 19
- 238000000926 separation method Methods 0.000 abstract description 9
- 230000035484 reaction time Effects 0.000 abstract description 7
- 238000005406 washing Methods 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract 1
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 20
- 238000006396 nitration reaction Methods 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000001117 sulphuric acid Substances 0.000 description 4
- 235000011149 sulphuric acid Nutrition 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides an isooctyl nitrate continuous preparation method and a reactor, the isooctyl nitrate continuous preparation method comprises the following steps: sulfuric acid with the mass concentration of 65 to 98% is continuously introduced into the reactor, nitric acid and isooctanol are simultaneously and continuously introduced into the reactor, an acid phase is flown out from one side of the upper part of the reactor, an ester phase is flown out from the other side of the reactor, the flown acid phase enters into a sulfuric acid circulation tank, the ester phase enters into a scrubber for washing processing, and a finished product is obtained by neutralizing, washing and drying. The molar ratio of sulfuric acid and nitric acid in the method is 2.5 to 3.8:1; the molar ratio of isooctanol and nitric acid is 1.05 to 1.15:1; the reaction temperature is 0-35 DEG C; the reaction time is 1-3 minutes; the used reactor has the following features: a cooling unit, a reaction unit and a separation unit are assembled in one; the isooctyl nitrate continuous preparation method has the following advantages: 1, continuous feeding and continuous discharge, 2, high intrinsic safety, 3, recycling sulfuric acid use, 4, high production efficiency, and 5, simple process, low investment, and low production costs.
Description
Technical field:
The present invention relates to the technical field of producing of petrochemicals isooctyl ester nitrate, be specifically related to a kind of continuous production processes and reactor of isooctyl ester nitrate.
Background technology
Isooctyl ester nitrate is a kind of diesel cetane-number improver of excellent property.The nitrated method of industrial general employing isooctyl alcohol is produced, and is catalyzer in production process with sulfuric acid, by nitric acid with isooctyl alcohol is directly nitrated in reactor obtains product isooctyl ester nitrate and water byproduct.The production reaction of nitric acid isooctyl is a typical strong quick inhomogeneous reaction of heat release, reaction process has following features: first, thermal discharge is large, when making nitrating agent with nitration mixture, sulfuric acid in nitration mixture is diluted by water generation reaction also releases the heat of dilution, and total heat effect of nitration reaction is about 700kJ/kg alcohol; The second, speed of response is fast, and when temperature is higher than 35 DEG C, reaction almost completes instantaneously; 3rd, reaction process is heterogeneous, the raw material isooctyl alcohol that density is lighter and nitric acid isooctyl in upper organic phase, nitric acid, sulfuric acid and water due to density comparatively focus on lower floor acid phase.4th, isooctyl ester nitrate can produce " self-accelerating reaction " in acid condition, makes runaway reaction.Therefore in the industrial production, enhancing mass and heat transfer efficiency, Reaction time shorten, to remove heat and is separated in acid system by the isooctyl ester nitrate of generation in time be in time the key ensureing process safety production and enhance productivity.
In patent report about the method for the different monooctyl ester of nitric acid synthesis, CN1031525A discloses a kind of method adopting mixed acid nitrification, this technique adopts injection-type reactor strengthening two-phase mixtures, icy salt solution is utilized to cool system and product, control reaction to carry out at lower temperature (10 ~ 25 DEG C) and speed, to ensure the security of process, yield is 95 ~ 97%; But shortcoming is there is larger potential safety hazard, namely carries out cooling after having reacted a large amount of reaction heat of generation and remove heat, careless manipulation or heat-eliminating medium transmission failure, easily cause temperature of charge in reactor sharply to rise, cause reactor to explode; A system production efficiency is not high again.CN1045773A discloses a kind of production technique, and advantage is without the need to additional cooling system, and temperature of reaction is carried out at 30 ~ 80 DEG C, must add stablizer urea and ammonium nitrate, residence time of material 50 minutes in reactor for suppressing side reaction; Shortcoming adopts tank reactor and hot water temperature control, there is the potential safety hazard of blast; Outer doping limits the recycle of sulfuric acid; Reaction times is longer, and system production efficiency is lower.CN1814581A discloses a kind of production technique, adds solvent oil, sherwood oil or halohydrocarbon as inert solvent in reaction process; Shortcoming is long reaction time, needs 0.5 ~ 1 hour, needs to adopt distil process to be separated with inert solvent by the isooctyl ester nitrate of generation after reaction terminates, and increases the danger of its production process, and increases energy consumption.CN101462962A discloses a kind of production technique and micro passage reaction, adopts micro passage reaction, reduces the content of sulfuric acid in nitration mixture, improves the security in production process; Shortcoming is that the Waste Sulfuric Acid produced in production process fails to recycle.CN101698646A discloses a kind of production technique, adopts micro-tubular reactor, realizes continuous prodution.Shortcoming is, temperature of reaction controls at 40 ~ 70 DEG C, and temperature of reaction system is higher, there is the possibility of " self-accelerating reaction ", and cause security risk, the Waste Sulfuric Acid produced in production process fails to recycle.CN103980125A discloses a kind of production technique, adopts micro passage reaction, solves the Recycling of Waste Sulfuric Acid in production process; Shortcoming is that Waste Sulfuric Acid recycles that need to be processed into concentration minimum be 90%, and the reaction times longer is 0.5 ~ 1 hour.
Summary of the invention
The object of the invention is: a kind of continuous production processes of isooctyl ester nitrate and the reactor used by this production technique are provided; Solve reaction times in existing production technique compared with long, that Waste Sulfuric Acid amount large, reaction system mass-transfer efficiency is low problem, to improve its economy; Solve the isooctyl ester nitrate problem that lifetime is long in acid system generated, to improve the intrinsic safety of its technological process.
For achieving the above object, the technical solution used in the present invention is: a kind of continuous production method of isooctyl ester nitrate, and its nitration reaction process is carried out in special reactor, comprises the steps:
A) start reactor, in reactor cooling unit, pass into refrigerant.
B) in reactor reaction unit, the sulfuric acid that mass concentration is 98% is passed into.
C) ratio being 2.5 ~ 3.8 in the mol ratio of sulfuric acid and nitric acid passes into the nitric acid that mass concentration is 97% in reactor reaction unit; The ratio being simultaneously 1.05 ~ 1.15 in the mol ratio of nitric acid and isooctyl alcohol passes into the isooctyl alcohol that mass concentration is 99.5% in reactor reaction unit.
D) regulate feed rate with control reaction mass in reactor the residence time at 1 ~ 3 minute.
E) regulate cold medium flux, the temperature in control reaction system is at 0 ~ 35 DEG C.
F) the sour phase of autoreactor heavy component outlet outflow, enter gathering separator and carry out oil-acid separation, oil phase (isooctyl ester nitrate crude product) goes the water washing of washer salt; Acid phase (dilute sulphuric acid) desulfuration acid circulation tank, recycles.
G) requirement recycling sulfuric acid is that mass concentration is between 65 ~ 98%.
H) the light phase of autoreactor Light ends outlet outflow, enter gathering separator and carry out oil-acid separation, oil phase (isooctyl ester nitrate crude product) goes washer water washing; Acid phase (dilute sulphuric acid) desulfuration acid circulation tank, recycles.
I) the isooctyl ester nitrate crude product going out washer again after being washed to neutrality, removes dry finished product through neutralizer neutralization.
As preferably, the mol ratio of sulfuric acid and nitric acid is 3.2: 1, and the mol ratio of nitric acid and isooctyl alcohol is 1.1: 1.
Reactor for realizing aforesaid method comprises cooling unit, reaction member and separating unit.
Cooling unit comprises the adapter of shell, inner drum, flow deflector and refrigerant entry/exit.
Reaction member comprises the adapter of motor, inner drum, rotary drum, bottom impeller and material entry/exit.
Separating unit comprises motor, rotary drum, blade, light phase collecting chamber, heavy phase collecting chamber, plate washer and Light ends go out adapter, heavy component goes out adapter.
Compared with prior art, the invention has the advantages that:
A) special reactor is adopted, realization response-cooling-separation one operate continuously.
B) realize the direct reuse of sulfuric acid, reduce and consume, increase economic efficiency.
C) adopt special reactor, realize sulfuric acid and isooctyl ester nitrate being directly separated in reactor.Greatly shorten the residence time of isooctyl ester nitrate in acid system, improve the intrinsic safety of technique.
D) adopt special reactor, enhance mass transfer effect, Reaction time shorten, improve the essential safety of technique, raise labour productivity.
Accompanying drawing explanation
Fig. 1 is the industrial flow chart of the continuous production embodiment of the method for a kind of isooctyl ester nitrate of the present invention.
Fig. 2 is the structural representation of the special reactor used in the present invention.
Embodiment
Now by reference to the accompanying drawings the present invention is described in further detail.These accompanying drawings are the schematic diagram of simplification, only basic structure of the present invention are described in a schematic way, and therefore it only shows the formation relevant with the present invention.
As shown in Figure 1, the invention provides a kind of continuous production method of isooctyl ester nitrate, comprise the following steps:
A) start reactor motor, the cooling unit to reactor passes into refrigerant.
B) by reaction mass residence time in reactor be 1.5 minutes setting flow.
C) to the reaction member of reactor, the sulfuric acid that mass concentration is 98% is pumped into.
D) when heavy phase is flowed out in the heavy component outlet of reactor, the ratio being 3.2 by the mol ratio of sulfuric acid and nitric acid pumps into the nitric acid of 97% in the reaction member of reactor.
E) ratio being 1.1 by the mol ratio of nitric acid and isooctyl alcohol pumps into the isooctyl alcohol of 99.5% in the reaction member of reactor.
F) regulate cold medium flux, control the temperature of reaction system at 10 ~ 15 DEG C.
G) heavy phase of autoreactor heavy component outlet outflow, enter gathering separator and carry out oil-acid separation, oil phase (isooctyl ester nitrate crude product) goes washer to wash; Acid phase (dilute sulphuric acid) desulfuration acid circulation tank, recycles.
H) the light phase of autoreactor Light ends outlet outflow, enter gathering separator and carry out oil-acid separation, oil phase (isooctyl ester nitrate crude product) goes washer to wash; Acid phase (dilute sulphuric acid) desulfuration acid circulation tank, recycles.
I) in washer, isooctyl ester nitrate crude product and water are uniformly mixed, and enter to assemble separator after washing away residual acid and carry out oil/water separation, lower floor's aqueous phase enters wastewater collection pond; Upper oil phase is that isooctyl ester nitrate crude product enters neutralizer.
J) aqueous sodium hydroxide solution adding 10% in neutralizer carries out neutralization reaction, and reaction solution enters to assemble separator and carries out oil/water separation, and lower floor's aqueous phase enters wastewater collection pond; Upper oil phase is that isooctyl ester nitrate crude product enters washer.
K) in washer, isooctyl ester nitrate crude product and water are uniformly mixed, and enter to assemble separator, carry out oil/water separation, and lower floor's aqueous phase enters wastewater collection pond; Upper oil phase is that neutral isooctyl ester nitrate crude product enters moisture eliminator.
L) in moisture eliminator, isooctyl ester nitrate crude product contacts with dry 4A molecular sieve, removes remaining moisture content, obtains finished product.Gained finished product, purity (GC) 99.5%, yield: 96.5%.
Claims (7)
1. a continuous production method for isooctyl ester nitrate, is characterized in that comprising the steps:
A) by mass concentration be 65 ~ 98% sulfuric acid pass into reactor continuously, then by mass concentration be 97% nitric acid and mass concentration be 99.5% isooctyl alcohol pass into reactor continuously simultaneously; In reactor, carry out the raw esterification of hybrid concurrency, realize being separated of sulfuric acid phase and isooctyl ester nitrate phase simultaneously.
B) sulfuric acid phase is flowed out in the side on autoreactor top, and after assembling and being separated, sulfuric acid flows into sulfuric acid circulation tank, again pumps into reactor, reuses, and a small amount of isooctyl ester nitrate flows into washed with water process; The opposite side on autoreactor top flows out isooctyl ester nitrate phase, and after assembling and being separated, a small amount of sulfuric acid flows into sulfuric acid circulation tank, and isooctyl ester nitrate flows into washed with water process; The isooctyl ester nitrate crude product going out washer is again through neutralization-washing--dry finished product.
2. the continuous production method of isooctyl ester nitrate as claimed in claim 1, is characterized in that: the vitriolated heavy phase of described bag enters gathering separator, separates a small amount of isooctyl ester nitrate, and sulfuric acid enters sulfuric acid circulation tank and recycles.
3. the continuous production method of isooctyl ester nitrate as claimed in claim 1, is characterized in that: the mass concentration of recycle sulfuric acid used is the sulfuric acid of 65 ~ 98%.
4. the continuous production method of isooctyl ester nitrate as claimed in claim 1, is characterized in that: the mol ratio of the sulfuric acid and nitric acid that pass into reactor is 2.5 ~ 3.8: 1; The mol ratio of nitric acid and isooctyl alcohol is 1.05 ~ 1.15: 1.
5. the continuous production method of isooctyl ester nitrate as claimed in claim 1, is characterized in that: temperature of reaction controls at 0 ~ 35 DEG C.
6. the continuous production method of isooctyl ester nitrate as claimed in claim 1, is characterized in that: the time that reaction mass stops in reactor is 1 ~ 3 minute.
7. the reactor used in the continuous production method of isooctyl ester nitrate as claimed in claim 1, is characterized in that: the reactor used comprises cooling unit, reaction member and separating unit; Described cooling unit comprises the adapter of shell, inner drum, flow deflector and refrigerant entry/exit; Described reaction member comprises the adapter of motor, inner drum, rotary drum, bottom impeller and material entry/exit; Described separating unit comprises motor, rotary drum, blade, light phase collecting chamber, heavy phase collecting chamber, plate washer and Light ends go out adapter, heavy component goes out adapter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510152100.0A CN105130818A (en) | 2015-03-25 | 2015-03-25 | Isooctyl nitrate continuous preparation method and reactor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510152100.0A CN105130818A (en) | 2015-03-25 | 2015-03-25 | Isooctyl nitrate continuous preparation method and reactor |
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| Publication Number | Publication Date |
|---|---|
| CN105130818A true CN105130818A (en) | 2015-12-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510152100.0A Pending CN105130818A (en) | 2015-03-25 | 2015-03-25 | Isooctyl nitrate continuous preparation method and reactor |
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| Country | Link |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109280007A (en) * | 2017-07-20 | 2019-01-29 | 中国石油化工股份有限公司 | A kind of method for continuously synthesizing of isooctyl ester nitrate |
| CN118812365A (en) * | 2024-07-02 | 2024-10-22 | 东营市海科瑞林化工有限公司 | A kind of synthetic method of 2-ethylhexyl nitrate |
-
2015
- 2015-03-25 CN CN201510152100.0A patent/CN105130818A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109280007A (en) * | 2017-07-20 | 2019-01-29 | 中国石油化工股份有限公司 | A kind of method for continuously synthesizing of isooctyl ester nitrate |
| CN118812365A (en) * | 2024-07-02 | 2024-10-22 | 东营市海科瑞林化工有限公司 | A kind of synthetic method of 2-ethylhexyl nitrate |
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Application publication date: 20151209 |