CN110437067A - The method for preparing cyclohexane cyclohexanedimethanodibasic ester - Google Patents
The method for preparing cyclohexane cyclohexanedimethanodibasic ester Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
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- C07C2601/14—The ring being saturated
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Abstract
The present invention relates to plasticizer preparation fields, and in particular to the preparation method of environment-friendly plasticizer cyclohexane alkane dicarboxylic acid esters.Method includes the following steps: (1) carries out hydrogenation reaction in fixed bed reactors, obtains cyclohexane cyclohexanedimethanodibasic ester crude product using the esterification crude product containing phthalic acid ester shown in formula (II) as hydrogenating materials,In formula (II), R1And R2It is identical or different, it is each independently selected from the alkyl of C1-C12；(2) cyclohexane cyclohexanedimethanodibasic ester crude product obtained by step (1) is subjected to refinement treatment, obtains cyclohexane cyclohexanedimethanodibasic ester product.The purifying process of hydrogenating materials is omitted in the method for the invention, and simplification of flowsheet improves product yield, reduces post-processing difficulty.
Description
Technical field
The present invention relates to plasticizer preparation fields, and in particular to the preparation method of environment-friendly plasticizer cyclohexane alkane dicarboxylic acid esters.
Background technique
Phthalates compound is widely used as the plasticizer (especially polyvinyl chloride (PVC)) of plastics.Example
Such as, the compound based on phthalic acid ester can be widely applied to electric appliance and electronic product, medicine, paint pigment, food containers, packaging
Material, lubricant, binder, surfactant, ceramic tile etc..But a large amount of zooperies prove, Long Term Contact phthalic acid esters
Peroxisome proliferation can be caused, and then induce liver tumour.Many countries have started to limit or forbid in medical instrument, food
Product, toy for children etc. in the plastic products of direct body contact use these phthalic easter plastizers.Therefore, one is found
The environmentally protective plasticizer that kind can be substituted for Phthalates is extremely urgent.
Phthalic acid ester can be converted into cyclohexane cyclohexanedimethanodibasic ester by benzene ring hydrogenation, and cyclohexane cyclohexanedimethanodibasic ester is a kind of
Environment-friendly plasticizer, it have with structure as Phthalates and performance, and function is more excellent.Specific manifestation are as follows: migration
Small, colorless and transparent, complete environmental protection, can be with common organic solvent and common plasticizers mutual tolerance, elasticity, the transparency, low temperature properties
Phthalic easter plastizer can be much better than, it is often more important that such product has excellent toxicological characteristics.Therefore, hexamethylene two
Formic acid ester plasticiser can be medical instrument, food packaging, medical supplies, toy for children and other and human body close contact PVC
Product manufacturer provides up the ideal solution of safety requirements, thus is forbidden to use the national ring of phthalic acid ester in many
Hexane dicarboxylic acid ester has been approved for food packaging, medical instrument and toy for children.
Currently, existing various phthalic acid ester hydrogenation techniques and catalyst technology, generally use stirred tank or fixed bed
Reaction pattern uses the noble metal catalyst based on Ru system or the non-precious metal catalyst based on Ni system.As adding hydrogen work
The raw material phthalic acid ester of sequence is both needed to refinement treatment, i.e., phthalic acid ester crude product is through thick dealcoholysis, alkali cleaning, washing, smart dealcoholysis, dry
Dry, decoloration and etc..Simultaneously, it is notable that the phthalic acid ester after refinement treatment has cracking etc. in hydrogenation process
Side reaction generates the by-products such as micro acid, acid anhydrides, alcohol, therefore cyclohexane cyclohexanedimethanodibasic ester crude product is still needed to carry out dealcoholysis and be taken off
Water step, in addition the technique that has also need alkali cleaning, washing and etc. be just able to satisfy product quality and require, eventually lead to hexamethylene diformazan
Acid esters production process is complicated, energy consumption is high, and cost is high, and this further restricts its Rapid Popularization and applications.
Summary of the invention
In order to overcome phthalic acid ester raw material used in prior art processes to need to refine, technique is cumbersome, higher cost
Problem, applicant of the present invention have found that one kind directly prepares hexamethylene as reaction raw materials using the esterification crude product of phthalic acid ester
The method of dicarboxylic acid esters.
The present invention provides a kind of method for preparing cyclohexane cyclohexanedimethanodibasic ester shown in formula (I), this method includes following step
It is rapid:
(1) using the esterification crude product containing phthalic acid ester shown in formula (II) as hydrogenating materials, in fixed bed reactors
Middle carry out hydrogenation reaction, obtains cyclohexane cyclohexanedimethanodibasic ester crude product,
In formula (I) and formula (II), R1And R2It is identical or different, it is each independently selected from the alkyl of C1-C12；
(2) cyclohexane cyclohexanedimethanodibasic ester crude product obtained by step (1) is subjected to refinement treatment, obtains cyclohexane cyclohexanedimethanodibasic ester and produces
Product.
The method of the invention directly enters hydrogenation process as hydrogenating materials to be esterified crude product, and hydrogenation products are again through refining
Process obtains product cyclohexane cyclohexanedimethanodibasic ester.Compared with prior art, esterification crude product needed for hydrogenation technique is omitted is de-
Operation links, the process flows such as alcohol, alkali cleaning, washing, smart dealcoholysis, dehydration, decoloration simplify, and plant investment, energy consumption significantly reduce；Ester
Change in crude product because containing a large amount of alcohol, can be used as hydrogenation reaction solvent, can effectively remove reaction heat, to reduce raw material and product
Pyrolysis side reaction, improve product yield, reduce post-processing difficulty；The method of the invention has low temperature, low pressure and low simultaneously
The mild hydrogenation condition of hydrogen ester molar ratio, not only equipment investment and operating cost are low, and can more give full play to catalyst activity,
Feed stock conversion and selectivity of product are all higher.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of method for preparing cyclohexane cyclohexanedimethanodibasic ester shown in formula (I), this method includes following step
It is rapid:
(1) using the esterification crude product containing phthalic acid ester shown in formula (II) as hydrogenating materials, in fixed bed reactors
Middle carry out hydrogenation reaction, obtains cyclohexane cyclohexanedimethanodibasic ester crude product,
In formula (I) and formula (II), R1And R2It is identical or different, it is each independently selected from the alkyl of C1-C12；
(2) cyclohexane cyclohexanedimethanodibasic ester crude product obtained by step (1) is subjected to refinement treatment, obtains cyclohexane cyclohexanedimethanodibasic ester and produces
Product.
In the present invention, the hydrogenating materials that the method uses are that the esterification containing phthalic acid ester shown in (II) slightly produces
Product, wherein R1And R2It is identical or different, it is each independently selected from the alkyl of C1-C12, such as can be methyl, ethyl, propyl, fourth
Base, isobutyl group, amyl, isopentyl, neopentyl, hexyl, isohesyl, heptyl, different heptyl, octyl, iso-octyl, nonyl, isononyl,
Decyl, isodecyl, undecyl or dodecyl.Above-mentioned phthalic acid ester crude product can be phthalic anhydride or (o-, m-, to) benzene two
The esterification crude product that esterification generates occurs with corresponding alcohol for formic acid.The esterification can be in condition commonly used in the art
Lower progress.
In the present invention, acid value≤0.6mgKOH/g of the hydrogenating materials, alcohol content control is ≤30%, water content control
System is ≤0.5%.
In the present invention, the fixed bed reactors are at least three, along the direction of logistics, set gradually to add hydrogen to protect
Protect reactor, pre-hydrogenator and main hydrogenator.
The method according to the present invention, the gas-liquid mixture fluid and pre-hydrogenator of the hydrogenation protecting reactor outlet
Enter pre-hydrogenator after the hydrogen mixing of entrance together, the gas-liquid mixture fluid of the pre-hydrogenator outlet adds with master
Enter main hydrogenator together after the hydrogen mixing of hydrogen reactor entrance.
In the present invention, in step (1), hydrogenation protecting agent is filled in the hydrogenation protecting reactor.
The hydrogenation protecting agent can be catalyst commonly used in the art.Preferably, the active group of the hydrogenation protecting agent
It is divided into Ni, carrier is water-fast acid proof porous material, such as can be with active carbon, silica etc., wherein is protected with described plus hydrogen
It protects on the basis of the total weight of agent, the content of simple substance Ni is 0.05-10.0%, preferably 0.5-4.5%.
In the present invention, it is filled with catalyst for pre-hydrogenation in the pre-hydrogenator, is filled in the main hydrogenator
It is filled with main hydrogenating catalyst, the catalyst for pre-hydrogenation and the main hydrogenating catalyst can be catalyst commonly used in the art,
It such as can be noble metal catalyst.Preferably, the active component of catalyst for pre-hydrogenation is one of Rh, Ru and Pd or several
Kind, carrier is selected from SiO2、TiO2One or more of with active carbon, on the basis of the total weight of the catalyst for pre-hydrogenation, institute
The content for stating active component is 0.3-2 weight %；The active component of main hydrogenating catalyst is one of Rh, Ru and Pd or several
Kind, it carries carrier and is selected from Al2O3、SiO2、TiO2One or more of with active carbon, with the total weight of the main hydrogenating catalyst
On the basis of, the content of the active component is 2-5 weight %.
The method according to the present invention, the hydrogenation protecting reactor purpose are mainly removed in phthalic acid ester crude product
Titanate catalyst, substance of easy coloring of entrainment etc., to protect the reactivity worth of catalyst for pre-hydrogenation and main hydrogenating catalyst
And service life.
The method according to the present invention, the operating condition of the hydrogenation protecting reactor are as follows: temperature is 40-80 DEG C, pressure
For 0.1-10MPa, on the basis of the total amount of phthalic acid ester in entrance raw material, weight (hourly) space velocity (WHSV) 0.5-10h-1, hydrogen ester molar ratio
For 0.1-5.0.
The method according to the present invention, the operating condition of the pre-hydrogenator are as follows: temperature is 50-120 DEG C, and pressure is
0.1-10MPa, on the basis of the total amount of phthalic acid ester in entrance raw material, weight (hourly) space velocity (WHSV) 0.5-8h-1, hydrogen ester molar ratio is
1.5-10。
The method according to the present invention, the operating condition of the main hydrogenator are as follows: temperature is 80-180 DEG C, and pressure is
0.1-10MPa, on the basis of the total amount of phthalic acid ester in entrance raw material, weight (hourly) space velocity (WHSV) 0.5-6h-1, hydrogen ester molar ratio is 2-
50。
In the present invention, it is preferred to which Gas-Liquid Dispersion process can be arranged before at least one described fixed bed reactors, use
It is distributed in hydrogenating materials in by hydrogen, forms the gas-liquid mixture fluid containing micro-bubble.The Gas-Liquid Dispersion process can be
Technological means commonly used in the art, such as can be static dissipation process or dynamic scatter process, preferably static dissipation process,
Further preferably using micro-nano pore membrane, micro-nano hole sieve plate, micro/nano level channel as the dispersion process of dispersed components thereof.
For example, hydrogen is micro-nano by average pore size when realizing dispersion process as dispersed components thereof using micro-nano pore membrane
The hole of size is injected into hydrogenating materials, forms the gas-liquid mixture fluid containing micro-bubble.In another example when with micro-nano hole
When sieve plate is that dispersed components thereof realizes dispersion process, after hydrogen passes through micro-nano hole sieve plate, adding for flowing is distributed to from vertical direction
In hydrogen feedstock, hydrogen and hydrogenating materials cross-flow passes, hydrogen cut into micro-bubble by the hydrogenating materials of cross-flow passes, and bubble is flat
Equal diameter can be controlled by bore dia on micro-nano hole sieve plate and hydrogen flow rate.For another example when with micro-nano
When grade channel is that dispersed components thereof realizes dispersion process, using arrangement of microspheres when in reaction channel, micron order and nanoscale are formed
The microchannel coexisted, each reactant form turbulent flow in microchannel, reach efficient mixed effect.
In the present invention, above-mentioned micro-nano hole, which refers to, had not only contained nano-pore but also had contained micron openings, the nano-pore in structure
Average diameter be 1-100nm, the average diameter of the micron openings is 100nm-2000 μm.In above-mentioned micro/nano level channel, receive
The average diameter in meter level channel is 1-100nm, and the average diameter of micro scale channel is 100nm-2000 μm.
In the present invention, after the liquid material and hydrogen mix, enter preferably in a manner of from bottom to top plus hydrogen is anti-
Device is answered to be reacted.
The method according to the present invention, in step (2), the refinement treatment includes: hydrogenation reaction product through thick dealcoholysis tower
It carries out dealcoholation treatment to alcohol content and is less than 1.5wt%, then again after alkali cleaning kettle, washing kettle carry out alkali cleaning, washing, through stripper
The remaining pure and mild low-boiling by-products of vacuum stripping removing, enter back into after vacuum flasher is dehydrated to qualification and obtain product.
The method according to the present invention adds the thick dealcoholysis, alkali cleaning of reaction product, washing process process after hydrogen that can pass through this
The conventional technical means in field is realized, such as can be carried out by the refinement treatment operating condition of phthalic acid ester crude product.
The method according to the present invention, the vacuum-stripping operation condition in the refinement treatment are as follows: water ester mass ratio is 1:
2-100, pressure 3KPa-90KPa, temperature are 100-140 DEG C.
According to the method for the present invention, the vacuum flashing operating condition in the refinement treatment are as follows: pressure 50KPa-90KPa,
Temperature is 90-120 DEG C.
In the actual production process, the step of the method for the invention (1) carries out in hydrogenation unit, and step (2) is in essence
It is carried out in unit processed.
Hydrogenation process can be directly embedded in esterification process and esterification products by the method according to the present invention, the technical process
After with corresponding alcohol esterification occurs for the centre of subtractive process, i.e. phthalic anhydride or (o-, m-, to) phthalic acid, directly with ester
Changing crude product is that hydrogenating materials enter hydrogenation process, and hydrogenation products through subtractive process, obtain product cyclohexane cyclohexanedimethanodibasic ester again.With
Prior art compares, and the method for the invention has the advantage that
(1) production equipment of traditional phthalate plasticisers can be used in the process, it is only necessary to be separately provided one
The switching of two kinds of products of phthalic acid ester and cyclohexane cyclohexanedimethanodibasic ester can be realized in a hydrogenation unit, i.e., ought need to produce benzene diformazan
When acid ester product, esterification crude product without hydrogenation unit but is directly entered refined unit；When needing to produce hexamethylene diformazan
When acid esters, esterification crude product is sent into hydrogenation unit, hydrogenation products, which enter back into refined unit, can be obtained cyclohexane cyclohexanedimethanodibasic ester
Product does not need that a set of production equipment is separately provided, more saving production cost；
(2) cyclohexane cyclohexanedimethanodibasic ester product is produced using the method for the invention, be omitted needed for traditional processing technology
It is esterified operation links, the process flows such as crude product dealcoholysis, alkali cleaning, washing, smart dealcoholysis, dehydration, decoloration to simplify, plant investment, energy
Consumption significantly reduces；
(3) it can be used as hydrogenation reaction solvent because containing a large amount of alcohol in the esterification of hydrogenating materials used in present invention crude product, can have
Effect removes reaction heat, so that the temperature of hydrogenation process catalytic bed be inhibited to increase and reduce bed hot(test)-spot temperature, it is former to reach reduction
The pyrolysis side reaction of material and product improves product yield, reduces post-processing difficulty；
(4) hydrogenation technique have low temperature, low pressure and low hydrogen ester molar ratio mild hydrogenation condition, not only equipment investment and
Operating cost is low, and can more give full play to catalyst activity, and feed stock conversion and selectivity of product are all higher.
The present invention will be described in detail by way of examples below.
Embodiment 1
Using the crude product diisooctyl phthalate after phthalic anhydride, isooctanol esterification as hydrogenating materials, the property of hydrogenating materials
Matter are as follows: acid value about 0.3mgKOH/g, isooctanol content about 23.6%, water content about 0.21%.The esterification crude product is sent with hydrogen
Enter hydrogenation unit and carries out hydrogenation reaction.
(1) hydrogenation unit
Hydrogenation protecting reactor (the hydrogenation protecting agent of filling is Ni/C (Ni content is 0.9%)), the front is provided with micro-
Nano-pore membrane (average diameter of nano-pore is 20nm, 800 μm of the average diameter of micron openings), hydrogen is high by micro-nano pore membrane
Degree is dispersed or dissolved in esterification crude product, forms about 700 μm of bubbles average diameter of gas-liquid mixture fluid): by the gas-liquid
Fluid-mixing injects hydrogenation protecting reactor from bottom to top.Operating condition therein are as follows: temperature is 70 DEG C, pressure 3.5MPa,
On the basis of the total amount of diisooctyl phthalate in entrance raw material, weight (hourly) space velocity (WHSV) 8h-1, hydrogen ester molar ratio is 0.3.
(catalyst for pre-hydrogenation of filling is Ru/TiO to pre-hydrogenator2(Ru content is 1.2%)), the front is provided with
Micro-nano hole sieve plate (average diameter of nano-pore is 50nm, 1000 μm of the average diameter of micron openings), by hydrogenation protecting reactor
The gas-liquid mixture fluid of outlet highly mixes in micro-nano hole sieve plate with hydrogen, forms about 900 μm of bubbles average diameter
Gas-liquid mixture fluid): the gas-liquid mixture fluid is injected into pre-hydrogenator from bottom to top.Operating condition therein are as follows: temperature
It is 80 DEG C, pressure 3.5MPa, on the basis of the total amount of diisooctyl phthalate in entrance raw material, weight (hourly) space velocity (WHSV) 6h-1,
Hydrogen ester molar ratio is 2.
(main hydrogenating catalyst of filling is Ru/Al to main hydrogenator2O3(Ru content is 2.6%)), the front is provided with
Micro-nano channel (average diameter of Nanoscale channels is 90nm, 1500 μm of the average diameter of micro scale channel), pre-add hydrogen is anti-
The gas-liquid mixture fluid for answering device to export highly mixes in micro-nano pore membrane with hydrogen, forms about 1200 μm of bubbles average diameter
Gas-liquid mixture fluid): the gas-liquid mixture fluid is injected into main hydrogenator from bottom to top.Operating condition therein are as follows: temperature
Degree is 90 DEG C, and pressure 3.5MPa, on the basis of the total amount of diisooctyl phthalate in entrance raw material, weight (hourly) space velocity (WHSV) is
4h-1, hydrogen ester molar ratio is 2.5.
After hydrogenated reaction, gas phase is recycled back to hydrogen generating system, and liquid product enters refined unit.Liquid phase composition are as follows: adjacent
Phthalic acid di-isooctyl content is 7ppm, cyclohexane cyclohexanedimethanodibasic di-isooctyl content about 76.82%, acid value about 0.12mgKOH/
G, isooctanol content are 22.5%, and water content 0.12%, remaining is pyrolysis product.The liquid phase is sent into vacuum tower and is slightly taken off
Alcohol, dealcoholysis to isooctanol content enter alkali cleaning kettle, lye Na less than 1.5%2CO3Solution, prevailing operating conditions are as follows: reaction temperature
85℃、Na2CO3Solution concentration 2%, lye/oil mass ratio are 1: 15, reenter washing kettle, washing conditions are as follows: 90 DEG C of temperature,
Water/oil mass ratio 1: 6 after washing, enters vacuum stripper essence dealcoholysis, stripper prevailing operating conditions: pressure 80KPa, raw material
110 DEG C of temperature, 120 DEG C of column bottom temperature, 105 DEG C of tower top temperature, water vapour/ester mass ratio are 1: 15, stripper top product
Through separating, organic phase is returned after can mixing with thick dealcoholysis overhead stream into esterification system, and stripping tower bottom distillate is sent into vacuum and is dodged
Tower is steamed, flash column prevailing operating conditions: 115 DEG C of pressure 45KPa, material temperature, dehydration product is product.The physics and chemistry of product
Matter is as shown in table 1 below.
Table 1
| Property | Product index |
| Platinum-cobalt method coloration | 14 |
| Acid value, mgKOH/g | 0.05 |
| Cyclohexane cyclohexanedimethanodibasic di-isooctyl content, % area | 99.78 |
| Water content, ppm | 170 |
| Octanol content, ppm | 76 |
| Diisooctyl phthalate, ppm | 7.2 |
| Product is along inverse ratio | 96.5/3.5 |
Embodiment 2
Using the crude product dioctyl terephthalate after terephthalic acid (TPA), octanol esterification as hydrogenating materials, hydrogenating materials
Property are as follows: acid value about 0.18mgKOH/g, octanol content about 28.2%, water content about 0.42%.The esterification crude product is sent with hydrogen
Enter hydrogenation unit and carries out hydrogenation reaction.
(1) hydrogenation unit
(the hydrogenation protecting agent of filling is Ni/SiO to hydrogenation protecting reactor2(Ni content is 2.3%), the front is provided with
Micro-nano hole sieve plate hydrogen high degree of dispersion or is dissolved in esterification crude product by micro-nano hole sieve plate, and it is average to form bubbles
The gas-liquid mixture fluid that about 850 μm of diameter): the gas-liquid mixture fluid is injected into hydrogenation protecting reactor from bottom to top, it is therein
Operating condition are as follows: temperature is 75 DEG C, pressure 5MPa, on the basis of the total amount of dioctyl terephthalate in entrance raw material, weight
When air speed be 5h-1, hydrogen ester molar ratio is 0.2.
(catalyst for pre-hydrogenation of filling is Pd-Ru/SiO to pre-hydrogenator2(Pd content is 0.2%, Ru content is
0.9%), the front is provided with micro-nano pore membrane, and the gas-liquid mixture fluid and hydrogen of hydrogenation protecting reactor outlet are micro-nano
Highly mixed in pore membrane, form about 950 μm of bubbles average diameter of gas-liquid mixture fluid): by gas-liquid mixture fluid from lower and
Upper injection pre-hydrogenator, operating condition therein are as follows: temperature be 85 DEG C, pressure 5MPa, in entrance raw material to benzene two
On the basis of the total amount of formic acid dioctyl ester, weight (hourly) space velocity (WHSV) 5h-1, hydrogen ester molar ratio is 2.8.
(main hydrogenating catalyst of filling is Rh-Ru/Al to main hydrogenator2O3(Rh content is 0.2%, Ru content is
2.2%), the front is provided with micro-nano pore membrane, by the gas-liquid mixture fluid of pre-hydrogenator outlet and hydrogen micro-nano
About 1100 μm of bubbles average diameter of gas-liquid mixture fluid is highly mixed to form in pore membrane): certainly by the gas-liquid mixture fluid
The main hydrogenator of lower and upper injection, operating condition therein are as follows: temperature is 105 DEG C, pressure 5MPa, with right in entrance raw material
On the basis of the total amount of dioctyl phthalate, weight (hourly) space velocity (WHSV) 3.5h-1, hydrogen ester molar ratio is 2.3.
After hydrogenated reaction, gas phase is recycled back to hydrogen generating system, and liquid product enters refined unit.Liquid phase composition are as follows: right
Dioctyl phthalate residual volume be 2ppm, cyclohexane cyclohexanedimethanodibasic dioctyl ester content about 72.21%, acid value about 0.10mgKOH/g,
Isooctanol content is 27.6%, and water content 0.13%, remaining is pyrolysis product.The liquid phase is sent into vacuum tower and carries out thick dealcoholysis,
Dealcoholysis, less than 1.5%, enters alkali cleaning kettle, lye Na to isooctanol content2CO3Solution, prevailing operating conditions are as follows: reaction temperature 90
℃、Na2CO3Solution concentration 2%, lye/oil mass ratio are 1: 25, reenter washing kettle, washing conditions are as follows: 85 DEG C of temperature, water/
The mass ratio 1: 7 of oil, after washing, enters vacuum stripper essence dealcoholysis, stripper prevailing operating conditions: pressure 75KPa, material temperature
110 DEG C, 120 DEG C of column bottom temperature, 105 DEG C of tower top temperature, water vapour/ester mass ratio be 1: 10, stripper top product through point
From, organic phase is returned after can mixing with thick dealcoholysis overhead stream into esterification system, and stripping tower bottom distillate is sent into vacuum flasher,
Flash column prevailing operating conditions: 110 DEG C of pressure 40KPa, material temperature, dehydration product is product.The physicochemical property of product is such as
Shown in the following table 2.
Table 2
| Property | Product index |
| Platinum-cobalt method coloration | 18 |
| Acid value, mgKOH/g | 0.04 |
| Cyclohexane cyclohexanedimethanodibasic dioctyl ester content, % area | 99.72 |
| Water content, ppm | 156 |
| Octanol content, ppm | 83 |
| Diisooctyl phthalate, ppm | 2.5 |
| Product is along inverse ratio | 95.2/4.8 |
Embodiment 3
Using the crude product M-phthalic acid dibutyl ester after M-phthalic acid, esterified by butyl alcohol as hydrogenating materials, hydrogenating materials
Property are as follows: acid value about 0.29mgKOH/g, butanol content about 29.3%, water content about 0.48%.The esterification crude product is sent with hydrogen
Enter hydrogenation unit and carries out hydrogenation reaction.
(1) hydrogenation unit
(the hydrogenation protecting agent of filling is Ni/TiO to hydrogenation protecting reactor2(Ni content is 2.8%), the front is provided with
Micro-nano hole sieve plate hydrogen high degree of dispersion or is dissolved in esterification crude product by micro-nano hole sieve plate, and it is average to form bubbles
The gas-liquid mixture fluid that about 750 μm of diameter): the gas-liquid mixture fluid is injected into hydrogenation protecting reactor from bottom to top, it is therein
Operating condition are as follows: temperature is 80 DEG C, pressure 3.0MPa, on the basis of the total amount of dioctyl isophthalate in entrance raw material,
Weight (hourly) space velocity (WHSV) is 8h-1, hydrogen ester molar ratio is 0.2.
(catalyst for pre-hydrogenation of filling is Pd-Rh/TiO to pre-hydrogenator2(Pd content is 0.2%, Rh content is
1.0%), the front is provided with micro-nano pore membrane, and the gas-liquid mixture fluid and hydrogen of hydrogenation protecting reactor outlet are micro-nano
Highly mixed in pore membrane, form about 860 μm of bubbles average diameter of gas-liquid mixture fluid): by gas-liquid mixture fluid from lower and
Upper injection pre-hydrogenator, operating condition therein are as follows: temperature is 85 DEG C, pressure 3.0MPa, with isophthalic in entrance raw material
On the basis of the total amount of diformazan dioctyl phthalate, weight (hourly) space velocity (WHSV) 8h-1, hydrogen ester molar ratio is 2.5.
(main hydrogenating catalyst of filling is Pd-Ru/TiO to main hydrogenator2(Pd content is 0.1%, Ru content is
3.0%, the front is provided with micro-nano pore membrane, and the gas-liquid mixture fluid and hydrogen of pre-hydrogenator outlet are in micro-nano pore membrane
Middle height is mixed to form about 950 μm of bubbles average diameter of gas-liquid mixture fluid): from bottom to top by the gas-liquid mixture fluid
Inject main hydrogenator, operating condition therein are as follows: temperature is 100 DEG C, pressure 3.0MPa, with isophthalic two in entrance raw material
On the basis of the total amount of formic acid dibutyl ester, weight (hourly) space velocity (WHSV) 4.0h-1, hydrogen ester molar ratio is 2.5.
After hydrogenated reaction, gas phase is recycled back to hydrogen generating system, and liquid product enters refined unit.Liquid phase composition are as follows:
Dibatyl phithalate residual volume is 1.5ppm, cyclohexane cyclohexanedimethanodibasic dibutyl ester content about 73.15%, acid value about 0.15mgKOH/
G, butanol content 26.67%, water content 0.12%, remaining is pyrolysis product.The liquid phase is sent into vacuum tower and carries out thick dealcoholysis,
Dealcoholysis, less than 1.5%, enters alkali cleaning kettle, lye Na to butanol content2CO3Solution, prevailing operating conditions are as follows: 90 DEG C of reaction temperature,
Na2CO3Solution concentration 2%, lye/oil mass ratio are 1: 25, reenter washing kettle, washing conditions are as follows: 90 DEG C of temperature, water/oil
Mass ratio 1: 7 after washing, enters vacuum stripper essence dealcoholysis, stripper prevailing operating conditions: pressure 75KPa, material temperature 115
DEG C, 125 DEG C of column bottom temperature, 105 DEG C of tower top temperature, water vapour/ester mass ratio be 1: 10, stripper top product through separating,
Organic phase is returned after can mixing with thick dealcoholysis overhead stream into esterification system, and stripping tower bottom distillate is sent into vacuum flasher, is dodged
Steam tower prevailing operating conditions: 115 DEG C of pressure 45KPa, material temperature, dehydration product is product.The physicochemical property of product is as follows
Shown in table 3.
Table 3
| Property | Product index |
| Platinum-cobalt method coloration | 20 |
| Acid value, mgKOH/g | 0.04 |
| Cyclohexane cyclohexanedimethanodibasic dibutyl ester content, % area | 99.78 |
| Water content, ppm | 165 |
| Butanol content, ppm | 90 |
| Between dibutyl phthalate, ppm | 15 |
| Product is along inverse ratio | 95.8/4.2 |
Embodiment 4
Using (dodecane) ester of crude product M-phthalic acid two after terephthalic acid (TPA), dodecanol esterification as hydrogenating materials,
The property of hydrogenating materials are as follows: acid value about 0.02mgKOH/g, butanol content about 29.3%, water content about 0.48%.The esterification slightly produces
Product and hydrogen are sent into hydrogenation unit and carry out hydrogenation reaction.
(1) hydrogenation unit
(the hydrogenation protecting agent of filling is Ni/TiO to hydrogenation protecting reactor2-SiO2(Ni content is 3.0%), the front is set
Be equipped with micro-nano hole sieve plate, by micro-nano hole sieve plate, hydrogen high degree of dispersion or be dissolved in esterification crude product in, formed bubbles
The gas-liquid mixture fluid that about 800 μm of average diameter): the gas-liquid mixture fluid is injected into hydrogenation protecting reactor from bottom to top,
In operating condition are as follows: temperature be 80 DEG C, pressure 6.0MPa, with the total amount of M-phthalic acid two (dodecane) in entrance raw material
On the basis of, weight (hourly) space velocity (WHSV) 4.5h-1, hydrogen ester molar ratio is 0.3.
(catalyst for pre-hydrogenation of filling is Ru/TiO to pre-hydrogenator2-SiO2(Ru content is 2.0%), the front is set
It is equipped with micro-nano pore membrane, the gas-liquid mixture fluid of hydrogenation protecting reactor outlet highly mixes in micro-nano pore membrane with hydrogen,
Form about 900 μm of bubbles average diameter of gas-liquid mixture fluid): gas-liquid mixture fluid is injected into pre-hydrotreating reaction from bottom to top
Device, operating condition therein are as follows: temperature is 90 DEG C, pressure 6.0MPa, with M-phthalic acid two (dodecane) in entrance raw material
Total amount on the basis of, weight (hourly) space velocity (WHSV) 4.5h-1, hydrogen ester molar ratio is 3.0.
(main hydrogenating catalyst of filling is Ru-Rh/TiO to main hydrogenator2-SiO2(Ru content is 3.0%, Rh content
For 0.3%), the front is provided with micro/nano level channel, and the gas-liquid mixture fluid and hydrogen of pre-hydrogenator outlet are in micro-nano
About 1000 μm of bubbles average diameter of gas-liquid mixture fluid is highly mixed to form in metre hole film): by the gas-liquid mixture fluid
Main hydrogenator, operating condition therein are injected from bottom to top are as follows: temperature is 105 DEG C, pressure 6.0MPa, with entrance raw material
On the basis of the total amount of middle M-phthalic acid two (dodecane) ester, weight (hourly) space velocity (WHSV) 4.0h-1, hydrogen ester molar ratio is 2.5.
After hydrogenated reaction, gas phase is recycled back to hydrogen generating system, and liquid product enters refined unit.Liquid phase composition are as follows:
Phthalic acid two (dodecane) ester residual volume is 1.7ppm, cyclohexane cyclohexanedimethanodibasic two (dodecane) ester content about 74.05%, acid value
About 0.10mgKOH/g, butanol content 25.73%, water content 0.14%, remaining is pyrolysis product.The liquid phase is sent into decompression
Tower carries out thick dealcoholysis, and dealcoholysis to butanol content enters alkali cleaning kettle, lye Na less than 1.5%2CO3Solution, prevailing operating conditions are as follows:
90 DEG C of reaction temperature, Na2CO3Solution concentration 2%, lye/oil mass ratio are 1: 25, reenter washing kettle, washing conditions are as follows: temperature
90 DEG C, water/oil mass ratio 1: 7 are spent, after washing, enters vacuum stripper essence dealcoholysis, stripper prevailing operating conditions: pressure
80KPa, 115 DEG C of material temperature, 120 DEG C of column bottom temperature, 105 DEG C of tower top temperature, water vapour/ester mass ratio are 1: 12, stripping
Through separating, organic phase returns after can mixing with thick dealcoholysis overhead stream into esterification system, stripping tower bottom distillate top of tower product
It is sent into vacuum flasher, flash column prevailing operating conditions: 110 DEG C of pressure 45KPa, material temperature, dehydration product is product.It produces
The physicochemical property of product is as shown in table 4 below.
Table 4
From above-described embodiment it is found that the method for the invention uses the esterification crude product of phthalic acid ester as raw material, save
The refinement treatment step for having omited traditional handicraft, simplifies process flow, simultaneously because in crude product a large amount of alcoholic solvents presence, subtract
The generation of side reaction is lacked, so that feed stock conversion is higher, product quality is preferable.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (10)
1. a kind of method for preparing cyclohexane cyclohexanedimethanodibasic ester shown in formula (I), method includes the following steps:
(1) using the esterification crude product containing phthalic acid ester shown in formula (II) as hydrogenating materials, in fixed bed reactors into
Row hydrogenation reaction obtains cyclohexane cyclohexanedimethanodibasic ester crude product,
In formula (I) and formula (II), R1And R2It is identical or different, it is each independently selected from the alkyl of C1-C12；
(2) cyclohexane cyclohexanedimethanodibasic ester crude product obtained by step (1) is subjected to refinement treatment, obtains cyclohexane cyclohexanedimethanodibasic ester product.
2. according to the method described in claim 1, wherein, the fixed bed reactors are at least three, along the direction of logistics,
It sets gradually as hydrogenation protecting reactor, pre-hydrogenator and main hydrogenator.
3. described according to the method described in claim 2, wherein, hydrogenation protecting agent is filled in the hydrogenation protecting reactor
The active component of hydrogenation protecting agent is Ni, and carrier is water-fast acid proof porous material.
4. described according to the method described in claim 2, wherein, catalyst for pre-hydrogenation is filled in the pre-hydrogenator
By main hydrogenating catalyst, the catalyst for pre-hydrogenation and the main hydrogenating catalyst are noble metal for filling in main hydrogenator
Catalyst.
5. according to the method described in claim 2, wherein, the active component of the noble metal catalyst is in Rh, Ru and Pd
It is one or more of.
6. according to the method in claim 2 or 3, wherein
The hydrogenation protecting reactor operating condition are as follows: temperature is 40-80 DEG C, pressure 0.1-10MPa, and hydrogen ester molar ratio is
0.1-5.0；
The pre-hydrogenator operating condition are as follows: temperature is 50-120 DEG C, pressure 0.1-10MPa, and hydrogen ester molar ratio is
1.5-10；
The main hydrogenator operating condition are as follows: temperature is 80-180 DEG C, pressure 0.1-10MPa, and hydrogen ester molar ratio is 2-
50。
7. according to the method described in claim 1, wherein, in step (2), the refinement treatment includes dealcoholysis, alkali cleaning, water
It washes, vacuum strips and flash-evaporation dehydration.
8. according to the method described in claim 5, wherein, the steam stripped operating condition of vacuum are as follows: water ester mass ratio is 1:2-
100, pressure 3KPa-90KPa, temperature are 100-140 DEG C；
The operating condition of the flash-evaporation dehydration are as follows: pressure 50KPa-90KPa, temperature are 90-120 DEG C.
9. according to the method described in claim 1, wherein, acid value≤0.6mgKOH/g of the hydrogenating materials, alcohol content≤
30%, water content≤0.5%.
10. according to the method described in claim 1, wherein, Gas-Liquid Dispersion process is provided with before the fixed bed reactors.
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