CN202186949U - Two-step hydrogenization process system for preparing neopentyl glycol - Google Patents
Two-step hydrogenization process system for preparing neopentyl glycol Download PDFInfo
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- CN202186949U CN202186949U CN 201120235436 CN201120235436U CN202186949U CN 202186949 U CN202186949 U CN 202186949U CN 201120235436 CN201120235436 CN 201120235436 CN 201120235436 U CN201120235436 U CN 201120235436U CN 202186949 U CN202186949 U CN 202186949U
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Abstract
The utility model provides a two-step hydrogenization process system for preparing neopentyl glycol, which comprises a first hydrogenation reactor and a second hydrogenation reactor, wherein the discharge opening of the first hydrogenation reactor is connected with the feed opening of the second hydrogenation reactor through a first vapor-liquid separator; and the discharge opening of the second hydrogenation reactor is connected with the inlet of a second vapor-liquid separator. Compared with the conventional process system, the two-step hydrogenization process system adopts two stages of hydrogenization process systems which are connected with each other in series, so as to almost converting HPA in an HPA solution obtained through condensation completely on a hydrogenization section; and the HPA has higher selectivity of NPG, which reaches not less than 97 percent.
Description
Technical field
The utility model relates to a kind of process system for preparing NSC 6366, relates to a kind of two step method hydrogenation technique system that is prepared NSC 6366 by the hydroxy pivalin aldehyde shortening concretely.
Background technology
NSC 6366 is important chemical intermediate, and NSC 6366 is mainly used in produces oil-free alkyd resin, polyester powder coating, unsaturated polyester resin, printing-ink, synthetic softening agent and aircraft oil etc.Have good thermostability, acid resistance, alkali resistance, weathering resistance.Be widely used in coating, building and insulating material industry, the NSC 6366 in the whole world 80% is used for coatings industry.
NSC 6366 is prepared by discrimination method and two kinds of methods of condensation hydrogenation method in industry usually.Discrimination method does; Use strong alkali catalyst, for example sodium hydroxide, Pottasium Hydroxide or calcium hydroxide make isobutyric aldehyde and formalin that aldol reaction take place under the basic catalyst effect and generate hydroxy pivalin aldehyde; Canizaro reaction takes place to intersect with excessive formaldehyde and generates NSC 6366 in hydroxy pivalin aldehyde again under strong alkaline condition; The oxidized generation formic acid of formaldehyde, in formic acid and the alkali with generate formate, reaction mixture is again through desalination, refining specification product.Yet the shortcoming of this method is to form a large amount of by product formate.
The condensation hydrogenation method does, at amine catalyst, especially triethylamine exists down, formaldehyde and isobutyric aldehyde reacted obtain NSC 6366, forms the principal product hydroxy pivalin aldehyde thus, and it is hydrogenation further, obtains the final product NSC 6366 of expecting thus.Also can carry out aldolization as catalyzer with anionite-exchange resin.
The catalyzer that has proposed many types is as hydrogenation catalyst.USP 4,250,337 proposed with barium for the copper chromite of its promotor as catalyzer.USP 4,855 is in 515; Adopt the promoted cupric oxide/copper chromite catalyst of manganese oxide, but its catalytic activity is lower slightly, hydrogenation need carry out under 160～170 ℃ condition; Yet raw material HPA solution decomposes under this temperature, causes the selectivity to NPG to reduce.
" carbon one chemical industry main products production technology " (Ying Weiyong, Cao Fahai, room ancient cooking vessel are already compiled) the 250th page: the not only active not enough and less stable of RaneyNi catalyzer, and Preparation of Catalyst and aftertreatment more complicated all; Cu-Cr catalyst is active same not enough; Hydrogenation reaction must at high temperature be carried out; Trace impurity in the raw material also can cause the poisoning of catalyst inactivation, and influences life of catalyst, simultaneously because catalyzer contains chromium; In Preparation of Catalyst, all must prevent the pollution of chromium in NPG production and the catalyzer last handling process.
Observe; Nickel catalyzator does not especially have gratifying effect being lower than under 100 ℃ the low relatively temperature; Hydroxy pivalin aldehyde transformation efficiency that obtains and NPG transformation efficiency do not reach the level that is enough to be used in commercial process when using nickel catalyzator; Because hydrogenation temperature is high, makes the amount of by product, particularly NSC 6366-mono isobutyrate and hydroxypivalyl hydroxypivalate sharply increase.The NSC 6366 of these deleterious by products and expection, particularly NSC 6366 mono isobutyrate are difficult to separate.And, because the amount of by-products increase reduces selectivity, so reduced the profit of manufacturing processed.In addition, when using lower temperature of reaction, need obvious more substantial catalyzer, thereby cause bigger process volume, and also significant prolongation of reaction times, these factors make this method not too suitable on technical scale.
Have only and use some noble metal catalyst, just obtained good relatively result.Therefore, for example, according to European patent 343 475, even under 80 ℃ temperature, use the catalyzer of platiniferous, nail and tungsten, the mixture that makes water or water and alcohol is as solvent." carbon one chemical industry main products production technology " (Ying Weiyong, Cao Fahai, room ancient cooking vessel are already compiled) the 250th page: noble metal catalyst has good activity and selectivity, but cost is expensive.
Usually in solvent phase, carry out the hydrogenation reaction of hydroxy pivalin aldehyde, moisture usually in the solution of HPA raw material.In hydrogenation reaction, water reduces selectivity.In addition, because high water content often destroys the grain pattern of catalyzer, so obviously descend the work-ing life of nickel catalyzator.
In the Chinese patent 98813171.4, embodiment 2, adopt methyl alcohol to make the solvent of hydroxy pivalin aldehyde; Silicon-dioxide is the Ni/Cr catalyzer of carrier, and at 70 ℃, the liquid feeding air speed is 2; Amounting to corresponding HPA air speed is 0.696, and the transformation efficiency of HPA is 93.2%, and selectivity is 99.7%.But its shortcoming adopts chromium-containing catalyst, be prone to produce during the preparation catalyzer and pollute, and reaction pressure is up to 70 crust.And this patent has been introduced methyl alcohol as solvent, in whole flow process, will inevitably increase the operation of the Separation and Recovery of methyl alcohol and product NPG like this, has improved energy consumption.In addition, it produces adverse influence to selectivity for fear of triethylamine in hydrogenation process, and its condensation operation adopts weak anion exchange resin catalyzer and since the performance of weak anion exchange resin catalyzer a little less than, need to use in a large number.
The technology that Chinese patent CN200910201434.7 proposes is: after the acetal step is accomplished; In hydrogenation process, selectivity is produced adverse influence for fear of triethylamine; Need isolate wherein aldolization catalyst and unreacted raw materials such as triethylamine; Then hydroxy pivalin aldehyde is mixed with certain density solution and sends into the hydrogenation reaction device, hydrogenation adopts Cu-series catalyst.Yet even adopt the method for vacuum distilling also to be difficult to eliminate fully the catalyzer such as triethylamine in the acetal gained solution, the HPA if methods such as employing crystallization, extraction are purified from the solution of acetal gained has bigger decline with the yield that makes HPA.Same this patent has also been introduced methyl alcohol as solvent, has increased the energy consumption of recycling methyl alcohol.
The utility model content
The purpose of the utility model is to overcome the deficiency of above prior art; A kind of two-step approach hydrogenation technique system for preparing NSC 6366 is provided; To be catalyzer carry out two step hydrogenation reactions to hydroxy pivalin aldehyde (HPA) to this process system makes NSC 6366 (NPG) with copper zinc-aluminium and copper zinc-aluminium manganese, can obtain high HPA transformation efficiency and high NPG selectivity.
For achieving the above object, the utility model adopts following technical scheme:
A kind of two-step approach hydrogenation technique system for preparing NSC 6366 is characterized in that, comprises first hydrogenator and second hydrogenator, and the discharge port of said first hydrogenator links to each other with the opening for feed of second hydrogenator through first vapour liquid separator; The discharge port of said second hydrogenator links to each other with the import of second vapour liquid separator.
The utility model carries out a step hydrogenation reaction to hydroxy pivalin aldehyde and makes the reaction of NSC 6366 of the prior art, is placed in placed in-line two hydrogenators and accomplishes, with the outlet material of first hydrogenator inlet feed as second hydrogenator.In first hydrogenator, wherein the catalyzer of filling under the situation of higher liquid air speed, the transformation efficiency of HPA >=85% but can not transform fully, HPA is to selectivity >=97% of NPG; In second hydrogenator, wherein the catalyzer of filling is under the situation of low liquid air speed, and HPA almost completely transforms, and the transformation efficiency of HPA is near 100%, and HPA is to selectivity >=97% of NPG.
As additional with further to the improvement of the above-mentioned process system that the utility model provided, the utility model can also adopt the following technical scheme or the combination of following technical scheme:
Further, the pneumatic outlet of said first vapour liquid separator is connected with first water cooler, and the pneumatic outlet of said second vapour liquid separator and liquid exit are connected with second water cooler and the 3rd water cooler respectively.
Further, the utility model also comprises the liquid stock reservoir, and said liquid stock reservoir is connected with the opening for feed of said first hydrogenator through first volume pump; The liquid exit of said first vapour liquid separator is connected with the opening for feed of second hydrogenator through second volume pump.
Further, the liquid exit of said first vapour liquid separator also is connected with the opening for feed of said first hydrogenator.The part of the discharging of said first hydrogenator is back to the inlet of first hydrogenator, as thinner with get into first hydrogenator again after liquid stock mixes; Another part of the discharging of first hydrogenator gets into second hydrogenator.
Further, said liquid stock reservoir also is connected with the opening for feed of said second hydrogenator through the 3rd volume pump.Can control the concentration of hydroxy pivalin aldehyde in the material that gets into said second hydrogenator like this, to improve the utilization ratio of second hydrogenator.When the hydroxy pivalin aldehyde content in the said first hydrogenator discharging is lower than this concentration; Can the concentration of hydroxy pivalin aldehyde in the material that gets into second hydrogenator be controlled in the above-mentioned scope through in the charging of second hydrogenator, sneaking into the said hydroxy pivalin aldehyde solution that obtains through aldolization.
Compare with existing process system, the utility model adopts the secondary hydrogenation technique system of polyphone, and the HPA solution that condensation is obtained almost completely transforms HPA in hydrogenation workshop section, and HPA has higher selectivity to NPG, reach >=97%.
Description of drawings
Fig. 1 is the two-stage hydrogenation process system schema of the utility model.
Embodiment
Further set forth the utility model below in conjunction with embodiment.Should be understood that these embodiment only are used to explain the utility model, and the scope of unrestricted the utility model.
The hydrogenation technique system of the utility model is as shown in Figure 1, and this hydrogenation technique system can make the HPA solution that obtains through aldolization almost completely transform HPA in the hydrogenation operation, and HPA has higher selectivity to NPG.The two-step approach hydrogenation technique system of this preparation NSC 6366 comprises that the discharge port of first hydrogenator 2 and second hydrogenator, 6, the first hydrogenators 2 links to each other with the opening for feed of second hydrogenator 6 through first vapour liquid separator 4; The discharge port of second hydrogenator 6 links to each other with the import of second vapour liquid separator 8.The pneumatic outlet of first vapour liquid separator 4 is connected with first water cooler 3.The pneumatic outlet of second vapour liquid separator 8 and liquid exit are connected with second water cooler 9 and the 3rd water cooler 7 respectively.Liquid stock reservoir 11 is connected with the opening for feed of first hydrogenator 2 through first volume pump 1; The liquid exit of first vapour liquid separator 4 is connected with the opening for feed of second hydrogenator 6 through second volume pump 5.The outlet of second volume pump 5 also is connected with the opening for feed of said first hydrogenator 2, so as with the part of the discharging of first hydrogenator 2 return as thinner with get into first hydrogenator 2 again after liquid stock mixes.Liquid stock reservoir 11 also is connected with the opening for feed of second hydrogenator 6 through the 3rd volume pump 10, with the concentration of hydroxy pivalin aldehyde in the material of said second hydrogenator 6 of control entering, improves the utilization ratio of second hydrogenator 6.H
2Source 12 is connected with the opening for feed of first hydrogenator 2 and second hydrogenator 6 respectively.
In the hydrogenation technique production process: the liquid stock in the liquid stock reservoir 11 gets into second hydrogenator 6 through volume pump 1 with the another part that gets into the discharging of first hydrogenator, 2, the first hydrogenators 2 after a part of returning charge of the discharging of first hydrogenator 2 mixes.If HPA concentration is very low in the discharging of first reactor drum 2,, can adopt volume pump 10 in the charging of second hydrogenator 6, to sneak into small number of materials liquid then in order to improve the utilization ratio of second hydrogenator 6.The outlet material of second hydrogenator 6 is after second vapour liquid separator 8 separates, and gas is through the 7 cooling back emptying of the 3rd water cooler, and liquid material obtains containing the solution of product NPG after second water cooler 9 cools off, and separation process such as warp distillation obtains product NPG again.
The utility model adopts the secondary hydrogenation technique system of above-mentioned polyphone, and the HPA solution that condensation is obtained almost completely transforms HPA in hydrogenation workshop section, and HPA has higher selectivity to NPG, reach >=97%.Further specify the beneficial effect of the utility model below through a concrete examples of industrial application.
The various processing parameters that carry out hydrogenation reaction in first hydrogenator are following:
In continuous trickle bed reactor, carry out the hydrogenation reaction of HPA, EE is described below:
Reactor drum: stainless steel tubular type reactor drum, internal diameter 10mm, length 400mm;
Catalyzer: Cu-Zn-Al, the coprecipitation method preparation contains cupric oxide 42wt%, zinc oxide 23.5wt%, aluminum oxide 33wt%, graphite 1.5wt% in the catalyzer, and catalyst powder is broken to 20～40 orders;
Charging: come free isobutyric aldehyde and formaldehyde to carry out the thick HPA solution without any purification operations that aldolization obtains, aldolization is used triethylamine catalysis;
The mixture of solvent: staple NPG and water (from the hydrogenation products returning charge);
Catalyst levels: 2.56g;
Liquid feed rate: 23.3g/hr;
Temperature: 141 ℃;
Pressure: 3.5MPa;
Air speed: WHSV=9.1hr
-1
Operating method: liquid stock warp first volume pump 1 in the liquid stock reservoir 11 is continuously pumped into and through first hydrogenator 2, uses excessive hydrogen.First hydrogenator, 2 temperature are controlled with the electric heater around the reactor enclosure.The liquid hydrogenation products that obtains from first hydrogenator 2 is done following the distribution: about 85wt% and free isobutyric aldehyde and formaldehyde carry out the reaction solution that aldolization obtains directly to be mixed; Be mixed with the raw material of first hydrogenator 2, rest part gets into second hydrogenator, 6 further hydrocrackings.
The character of the incoming flow of first hydrogenator 2 and product component is shown in the following table 1 under the steady state conditions.
Table 1
The second hydrogenator EE is described below:
In continuous trickle bed reactor, carry out the hydrogenation reaction of HPA;
Reactor drum: stainless steel tubular type reactor drum, internal diameter 10mm, length 400mm;
Catalyzer: Cu-Zn-Al-Mn, the coprecipitation method preparation contains cupric oxide 40wt%, zinc oxide 22.5wt%, aluminum oxide 31wt%, manganese oxide 5%, graphite 1.5wt% in the catalyzer, and catalyst powder is broken to 20～40 orders;
Charging: the product of the hydrogenation reaction that obtains by embodiment 1;
Catalyst levels: 2.52g;
Liquid feed rate: 12.6g/hr;
Temperature: 141 ℃;
Pressure: 3.5MPa;
Air speed: WHSV=5hr
-1
The character of the incoming flow of second hydrogenator 6 and product component is shown in the following table 2 under the steady state conditions.
Table 2
The selectivity of the NPG that calculates from product analysis is 96%, and the transformation efficiency of HPA is 100%.
Through first hydrogenator, second hydrogenator, the total transformation efficiency of two step hydrogenation HPA is nearly 100%, total selectivity 98.65% (in HPA, not comprising the HPHP hydrogenation).
Claims (6)
1. a two-step approach hydrogenation technique system for preparing NSC 6366 is characterized in that, comprises first hydrogenator and second hydrogenator, and the discharge port of said first hydrogenator links to each other with the opening for feed of second hydrogenator through first vapour liquid separator; The discharge port of said second hydrogenator links to each other with the import of second vapour liquid separator.
2. the two-step approach hydrogenation technique system of preparation NSC 6366 as claimed in claim 1; It is characterized in that; The pneumatic outlet of said first vapour liquid separator is connected with first water cooler, and the pneumatic outlet of said second vapour liquid separator and liquid exit are connected with second water cooler and the 3rd water cooler respectively.
3. the two-step approach hydrogenation technique system of preparation NSC 6366 as claimed in claim 1 is characterized in that, also comprises the liquid stock reservoir, and said liquid stock reservoir is connected with the opening for feed of said first hydrogenator through first volume pump; The liquid exit of said first vapour liquid separator is connected with the opening for feed of second hydrogenator through second volume pump.
4. like the two-step approach hydrogenation technique system of arbitrary described preparation NSC 6366 among the claim 1-3, it is characterized in that the liquid exit of said first vapour liquid separator also is connected with the opening for feed of said first hydrogenator.
5. like the two-step approach hydrogenation technique system of arbitrary described preparation NSC 6366 among the claim 1-3, it is characterized in that said liquid stock reservoir also is connected with the opening for feed of said second hydrogenator through the 3rd volume pump.
6. the two-step approach hydrogenation technique system of preparation NSC 6366 as claimed in claim 5 is characterized in that, said liquid stock reservoir also is connected with the opening for feed of said second hydrogenator through the 3rd volume pump.
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| CN 201120235436 CN202186949U (en) | 2011-07-06 | 2011-07-06 | Two-step hydrogenization process system for preparing neopentyl glycol |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112920016A (en) * | 2021-01-27 | 2021-06-08 | 浙江恒澜科技有限公司 | Preparation device and method of 1, 3-propylene glycol crude product solution |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112920016A (en) * | 2021-01-27 | 2021-06-08 | 浙江恒澜科技有限公司 | Preparation device and method of 1, 3-propylene glycol crude product solution |
| CN112920016B (en) * | 2021-01-27 | 2022-07-08 | 浙江恒逸石化研究院有限公司 | Preparation device and method of 1, 3-propylene glycol crude product solution |
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Legal Events
| Date | Code | Title | Description |
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| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: SHANGHAI HUAYI ENERGY + CHEMICAL INDUSTRY CO., LTD Free format text: FORMER NAME: SHANGHAI COKING CO., LTD. |
|
| CP01 | Change in the name or title of a patent holder |
Address after: 200241 Minhang District, Wu Long Road, No. 4280, Shanghai Patentee after: Shanghai Hua Yi derived energy chemical Co., Ltd Address before: 200241 Minhang District, Wu Long Road, No. 4280, Shanghai Patentee before: Shanghai Coking Co., Ltd. |
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| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20120411 |