CN104119199A - Deacidification method for hanging type tetrahydrodicyclopentadiene - Google Patents
Deacidification method for hanging type tetrahydrodicyclopentadiene Download PDFInfo
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- CN104119199A CN104119199A CN201410340068.4A CN201410340068A CN104119199A CN 104119199 A CN104119199 A CN 104119199A CN 201410340068 A CN201410340068 A CN 201410340068A CN 104119199 A CN104119199 A CN 104119199A
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- deacidification
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- hanging type
- stripping method
- acid stripping
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Abstract
The invention discloses a deacidification method for hanging type tetrahydrodicyclopentadiene. The deacidification method comprises the following steps: adding a solid neutralizer into the hanging type tetrahydrodicyclopentadiene which is obtained by bridge type tetrahydrodicyclopentadiene isomerization reaction to carry out deacidification neutralizing treatment; and after deacidification neutralizing treatment is completed, removing solid waste residue to realize deacidification treatment on the hanging type tetrahydrodicyclopentadiene, wherein a catalyst for the bridge type tetrahydrodicyclopentadiene isomerization reaction is AlCl3, and the solid neutralizer is a solid alkali metal hydroxide. Compared with an existing aqueous alkali repeated-washing neutralization method, the deacidification method disclosed by the invention has the following advantages that a product treated by the solid neutralizer is less in chlorine content and low in acidity, and does not cause corrosion interferences on equipment in a subsequent distillation process. The neutralizer does not contain water, and does not generate emulsification with the product, the yield of neutralized product is high. In the absence of water, the deacidification method saves water resources, and does not produce wastewater which is difficult to treat. Besides, the deacidification method is simple in flow, less in corollary equipment and low in equipment investment and operation cost.
Description
Technical field
The acid stripping method that the present invention relates to a kind of hanging type tetrahydrochysene dicyclopentadiene, belongs to chemical production technical field.
Background technology
Hanging type tetrahydrochysene dicyclopentadiene (exo-THDCPD, have another name called JP-10) there is the features such as lower zero pour (79 DEG C), suitable flash-point (55 DEG C), high volume calorific value and hypotoxicity, be a kind of high density liquid hydrocarbon fuel of excellent property.
The synthetic of hanging type tetrahydrochysene dicyclopentadiene carries out through hydrogenation, isomerization two steps conventionally.First be reduced to bridge-type tetrahydro-dicyclopentadiene (endo-THDCPD) by dicyclopentadiene hydrogenated, then by bridge-type tetrahydro-dicyclopentadiene under the effect of acid catalyst, isomery turns to hanging type tetrahydrochysene dicyclopentadiene.Anhydrous AlCl
3being to commonly use the most, is also the most effective bridge-type tetrahydro-dicyclopentadiene isomery conversion catalyst, and reaction conversion ratio is high, and hanging isomer selectivity is good.
In isomerization reaction, AlCl
3with bridge-type tetrahydro-dicyclopentadiene and the mutual complexing of product J P-10, play acid catalyst effect.For fear of AlCl
3etching apparatus in the rectified purified process of product, also considers the finished product Cl ion and acidity standard-required, need to after isomerization reaction finishes, carry out depickling dechlorination to product and process.
Depickling is processed conventionally and is used containing alkali aqueous solution and acid reaction product and carry out neutralization reaction, waste residue Al (OH)
3remove by filter, Cl ion separates and removes in the aqueous solution with chlorate form.The shortcoming of this treatment process is, storage and conveying equipment are various, alkali aqueous solution and oil product generation emulsification, and when oily water separation, product loss affects yield.Alkali lye neutralisation water loss is large, and produce a large amount of waste water be difficult to process.
Summary of the invention
The object of this invention is to provide a kind of acid stripping method of hanging type tetrahydrochysene dicyclopentadiene, acid stripping method of the present invention, uses solid alkali as neutralizing agent, and technical process is simple, and equipment investment is few, and process cost is low; N-process does not make water or alkali lye, has saved valuable water resources, and does not produce reluctant waste water, AlCl
3neutralization online in reactor, the neutral slag charge of generation is easy to process; With energy saving technology environmental protection, simple to operate, safe in whole.
The acid stripping method of hanging type tetrahydrochysene dicyclopentadiene provided by the present invention, comprises the steps:
To reacting in the hanging type tetrahydrochysene dicyclopentadiene obtaining and add solid neutralizing agent through isomerization of bridge-type tetrahydro-dicyclopentadiene, carry out depickling neutralizing treatment; After described depickling neutralizing treatment completes, remove solid slag and realize the depickling processing to hanging type tetrahydrochysene dicyclopentadiene;
The catalyzer of described isomerization of bridge-type tetrahydro-dicyclopentadiene reaction is AlCl
3;
Described solid neutralizing agent is solid alkali metal oxyhydroxide.
In above-mentioned acid stripping method, described solid neutralizing agent is Ca (OH)
2, Ba (OH)
2, Mg (OH)
2, NaOH or KOH.
In above-mentioned acid stripping method, the condition of described depickling neutralizing treatment is:
Pressure can be 1atm～5.0MPa, specifically can be 1.0MPa;
Temperature can be 60 DEG C～120 DEG C, specifically can be 75 DEG C or 95 DEG C;
Stirring velocity can be 200rpm～1000rpm, specifically can be 600rpm;
Time can be 0.5h～5h, specifically can be 2h.
In above-mentioned acid stripping method, the add-on of described solid neutralizing agent can be AlCl
31～8 times of quality, specifically can be AlCl
32 times of quality.
In above-mentioned acid stripping method, by the mode of filtration or sedimentation, described solid slag is removed.
In above-mentioned acid stripping method, the service temperature of described filtering unit can be 20 DEG C～90 DEG C, and operation pressure drop can be 10kpa～100kpa, specifically can under the condition of 30 DEG C and 0.3bar, carry out.
In above-mentioned acid stripping method, the service temperature of described sedimentation device can be 20 DEG C～90 DEG C, and operation pressure drop can be 0.1MPa～1MPa, specifically can under the condition of 30 DEG C and 0.3MPa, carry out.
Identical with Chinese patent application 201210433414.4 of the condition of isomerization of bridge-type tetrahydro-dicyclopentadiene reaction, as the temperature of isomerization reaction can be 70 DEG C～120 DEG C, pressure can be 0～3.0MPa, and the time can be 5min～120min; Specifically can under hydrogen atmosphere or nitrogen atmosphere, carry out; And carry out under the condition that is 400rpm～1200rpm at mixing speed.
Prepare the raw material of hanging type tetrahydrochysene dicyclopentadiene and specifically can select technical grade dicyclopentadiene (DCPD), it contains DCPD approximately 83% left and right conventionally, or selects highly purified dicyclopentadiene (DCPD), and DCPD is about more than 96%.
Compared with the neutralization method that the present invention washes repeatedly with existing alkali aqueous solution, have the following advantages:
(1) after solid neutralizing agent is processed, product chlorinity is few, and acidity is low, and follow-up rectifying process device is not caused to infection.
(2) neutralizing agent is not moisture, not can with product generation emulsifying effect, neutralized product yield is high.
(3) this technique does not have the participation of water, saves water resources, does not produce reluctant waste water.Flow process is simple, and support equipment is few; Facility investment and running cost are low.
(4) this technique neutral temperature is low, and energy consumption is little, and processing safety is high.
Embodiment
The experimental technique using in following embodiment if no special instructions, is ordinary method.
Material, reagent etc. used in following embodiment, if no special instructions, all can obtain from commercial channels.
Industry DCPD or high purity DCPD raw material are according to the secondary hydrogenation process in Chinese patent application 201210433414.4, the bridge-type tetrahydro-dicyclopentadiene product of gained is joined in isomerization reaction still, continue to carry out isomerization reaction by isomerisation conditions in Chinese patent application 201210433414.4.
By isomerization product material unload in and in still, add solid neutralizing agent, control the neutrality condition such as neutral temperature, pressure and stir speed (S.S.).After N-process finishes, product carries out the test of acidity and Cl content, and wherein GB GB/T264 petroleum product acid value measuring method is carried out in acidity analysis, and Cl content analysis is carried out content of organic chloride measuring method in GB GB/T18612 crude oil.
In embodiment reactor and in and still be 1L Autoclave, in practice, be not limited to the reactor of this volume.
The solid neutralizing agent using in embodiment is solid Ca (OH)
2, in practice, be not limited to this solid neutralizing agent.
In embodiment, neutralization reaction pressure is selected 1.0MPa, is not limited to this reaction pressure in practice.
In embodiment, the neutralization reaction time is elected 2h as, is not limited to this reaction times in practice.
The raw material using in embodiment, for DCPD content is respectively 83% technical grade DCPD and 96% high purity DCPD, is not limited to this two classes raw material in practice.
In embodiment, in DCPD raw material, normal heptane solvent mass content is 25%, adopts solvent to be not limited to normal heptane in practice, and solvent quality content is also not limited to 25%.
Raw material service condition in the each embodiment of table 1 and in and still use-pattern
Neutralization reaction condition in the each embodiment of table 2
The reaction result of the each embodiment of table 3
Can be learnt by the data in table 3, technical grade DCPD or high purity DCPD are the thick product of the synthetic hanging type tetrahydrochysene dicyclopentadiene of raw material, through in the solid under above-mentioned reaction conditions and after technique depickling dechlorination, the acidity of product can drop to 0, Cl content and drop to below 13ppm.
Claims (7)
1. an acid stripping method for hanging type tetrahydrochysene dicyclopentadiene, comprises the steps:
To reacting in the hanging type tetrahydrochysene dicyclopentadiene obtaining and add solid neutralizing agent through isomerization of bridge-type tetrahydro-dicyclopentadiene, carry out depickling neutralizing treatment; After described depickling neutralizing treatment completes, remove solid slag and realize the depickling processing to hanging type tetrahydrochysene dicyclopentadiene;
The catalyzer of described isomerization of bridge-type tetrahydro-dicyclopentadiene reaction is AlCl
3;
Described solid neutralizing agent is solid alkali metal oxyhydroxide.
2. acid stripping method according to claim 1, is characterized in that: described solid neutralizing agent is Ca (OH)
2, Ba (OH)
2, Mg (OH)
2, NaOH or KOH.
3. acid stripping method according to claim 1 and 2, is characterized in that: the condition of described depickling neutralizing treatment is:
Pressure is 1atm～5.0MPa;
Temperature is 60 DEG C～120 DEG C;
Stirring velocity is 200rpm～1000rpm;
Time is 0.5h～5h.
4. according to the acid stripping method described in any one in claim 1-3, it is characterized in that: the add-on of described solid neutralizing agent is AlCl
31～8 times of quality.
5. according to the acid stripping method described in any one in claim 1-4, it is characterized in that: the mode by filtration or sedimentation is removed described solid slag.
6. acid stripping method according to claim 5, is characterized in that: the service temperature of described filtering unit is 20 DEG C～90 DEG C, and operation pressure drop is 10kpa～100kpa.
7. acid stripping method according to claim 5, is characterized in that: the service temperature of described sedimentation device is 20 DEG C～90 DEG C, and operation pressure drop is 0.1MPa～1MPa.
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|---|---|---|---|
| CN201410340068.4A CN104119199A (en) | 2014-07-16 | 2014-07-16 | Deacidification method for hanging type tetrahydrodicyclopentadiene |
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|---|---|---|---|
| CN201410340068.4A CN104119199A (en) | 2014-07-16 | 2014-07-16 | Deacidification method for hanging type tetrahydrodicyclopentadiene |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4086286A (en) * | 1976-09-03 | 1978-04-25 | Suntech, Inc. | Isomerization of tetrahydropolycyclopentadienes to a missile fuel additive |
| JP2003128593A (en) * | 2001-10-18 | 2003-05-08 | Nippon Zeon Co Ltd | Method for producing exo-tetrahydrodicyclopentadiene |
| CN102924216A (en) * | 2012-11-02 | 2013-02-13 | 中科合成油技术有限公司 | Synthetic method for exo-tetrahydrodicyclopentadiene (THDCPD) |
| CN103739422A (en) * | 2014-01-27 | 2014-04-23 | 锦州康泰润滑油添加剂股份有限公司 | Preparation method of dialkyl benzene |
-
2014
- 2014-07-16 CN CN201410340068.4A patent/CN104119199A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4086286A (en) * | 1976-09-03 | 1978-04-25 | Suntech, Inc. | Isomerization of tetrahydropolycyclopentadienes to a missile fuel additive |
| JP2003128593A (en) * | 2001-10-18 | 2003-05-08 | Nippon Zeon Co Ltd | Method for producing exo-tetrahydrodicyclopentadiene |
| CN102924216A (en) * | 2012-11-02 | 2013-02-13 | 中科合成油技术有限公司 | Synthetic method for exo-tetrahydrodicyclopentadiene (THDCPD) |
| CN103739422A (en) * | 2014-01-27 | 2014-04-23 | 锦州康泰润滑油添加剂股份有限公司 | Preparation method of dialkyl benzene |
Non-Patent Citations (1)
| Title |
|---|
| 杨靖华等: "乙烯裂解C9馏分制备溶剂油", 《涂料工业》 * |
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Application publication date: 20141029 |
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