CN101168497A - Method for producing methyl isopropyl ketone - Google Patents
Method for producing methyl isopropyl ketone Download PDFInfo
- Publication number
- CN101168497A CN101168497A CNA2006101174824A CN200610117482A CN101168497A CN 101168497 A CN101168497 A CN 101168497A CN A2006101174824 A CNA2006101174824 A CN A2006101174824A CN 200610117482 A CN200610117482 A CN 200610117482A CN 101168497 A CN101168497 A CN 101168497A
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- China
- Prior art keywords
- catalyst
- catalyzer
- isoprene
- methyl isopropyl
- isopropyl ketone
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Abstract
The invention relates to a process for producing methyl isopropylacetone, which uses H3PO4-B/ bergmeal as catalyst, converts isoprene and water in a thermal-insulation reactor into methyl isopropylacetone. The process comprises that gasified water and isoprene are preheated, to be fed into a catalyst bed via the top of the reactor to react, wherein the phosphate content of the catalyst is 50-80% of catalyst mass, while the boron content is 4-9%. When the reaction temperature is 180-300DEG C, the mol ratio between water and isoprene is 4.0-8.0, air-speed LHSV is 0.1-0.5h-1, and the reaction pressure is normal pressure as 0.3MPa, isoprene and water via addition and isomerization generate methyl isopropylacetone. Compared with prior H3PO4 bergmeal catalyst, the invention uses H3PO4-B bergmeal catalyst to improve catalyst stability and effectively overcome the defects of H3PO4-B bergmeal catalyst as intrinsic easy phosphate loss and catalyst pelitization, to prolong the service life of catalyst, thereby reducing the catalyst application cost and production cost of methyl isopropylacetone.
Description
Technical field
The present invention relates to a kind of is the method for feedstock production methyl isopropyl Ketone with the isoprene, particularly makes isoprene and water, at H
3PO
4Under the effect of-B/ diatomite an acidic catalyst, isoprene is through a kind of method of hydration and isomerization reaction production methyl isopropyl Ketone.
Background technology
Methyl isopropyl Ketone (Methyl isopropyl ketone, hereinafter to be referred as MIPK) be a kind of water white transparency, fine-chemical intermediate and high-grade solvent with aromatic odour are mainly used in preparation acrylic fibers special-purpose cationic dyestuff intermediate three training departments and medicine, spices intermediate.The synthetic of MIPK can be adopted multiple route, but the technology with industrial significance mainly contains three kinds of the condensation isomerization processes of decarboxylation technology that isopropylformic acid and acetate are raw material, methyl ethyl ketone and isoprene direct hydration isomerization processes.Decarboxylation technology is higher because of raw material consumption, complex manufacturing, and raw material has bigger corrodibility to equipment, exists the higher and problem of environmental pollution of production cost; The condensation isomerization processes of methyl ethyl ketone is then because a large amount of propiones and the deficiency that needs to react under the high temperature of by-product, restricted further developing of this technology, and isoprene direct hydration isomerization processes, source and production cost from the advance of production technique, quality product, raw material, particularly from the influence to environment, this technology has remarkable advantages.
Because isoprene just is very easy to polymerization reaction take place when not having catalyzer, therefore can infer and use H
3PO
4Under/diatomite catalyzer and the 220 ℃ of hot conditionss, isoprene can polymerization reaction take place.Influence catalyst activity and stability.
At catalyst surface, when isoprene hydration rate during obviously faster than isoprene polymerization speed, this moment, catalyzer was slower because of coking and deactivation speed; When two speed of reaction near the time because the catalyst surface polymer content constantly increases, make that catalyst activity continues to descend, this moment, catalyst stability was relatively poor.The speed of isoprene hydration rate and rate of polymerization removes outside the Pass catalytic performance with catalyzer self has, and is also relevant with water/isoprene mol ratio, temperature of reaction in the raw material.Therefore, from technological angle, reasonably temperature of reaction and water/isoprene mol ratio are favourable work-ing life to improving catalyzer.
At H
3PO
4The quantity of/diatomite catalyst surface free phosphoric acid and composition decision catalyst activity height, the catalyst surface free phosphoric acid mainly is made up of ortho-phosphoric acid, tetra-sodium and a small amount of Tripyrophosphoric acid, preceding two kinds of phosphoric acid can provide the middle and high intensity acid site of some amount, be the reactive activity position, Tripyrophosphoric acid is non-active site then.But when the isoprene hydration,, make catalyst activity be and reduce trend gradually,, thereby have a strong impact on the work-ing life of catalyzer simultaneously because the structural damage meeting obviously reduces the intensity of catalyzer because catalyst surface institute phosphoric acid can be taken out of gradually by material.
GB9904343 discloses the technology that is prepared methyl isopropyl Ketone by the isoprene hydration.At 200～300 ℃, LHSV is 0.33h
-1, use phosphoric acid quality mark is 40%～60% H
3PO
4During/diatomite catalyzer, the methyl isopropyl Ketone yield is 63%.
(petrochemical complex, 1999,28 (11): such as Chen Suhong 769-771) to mixed C
5Fraction.Use H
3PO
4/ diatomite Preparation of Catalyst methyl isopropyl Ketone technology is studied.Be 65% at the pickling massfraction of catalyzer, 220 ℃ of temperature of reaction, water/C
5Mol ratio is 6.2, LHSV is 0.32h
-1The time, the yield of methyl isopropyl Ketone is 66%, and selectivity is 83%, and the transformation efficiency of isoprene is 80%.But catalyzer can only use about one month.
In above technical scheme, though can production methyl isopropyl Ketone product, because H
3PO
4The defective of easy loss of/diatomite catalyzer inherent phosphoric acid and the easy argillization of catalyzer makes catalyzer long period to use, and catalyzer needs to change continually.
Summary of the invention
Purpose of the present invention is exactly the production method that a kind of methyl isopropyl Ketone is provided for the defective that overcomes above-mentioned prior art existence.
Purpose of the present invention can be achieved through the following technical solutions:
The production method of methyl isopropyl Ketone, this method adopts H
3PO
4-B/ diatomite catalyzer makes isoprene and water be converted into methyl isopropyl Ketone in adiabatic reactor.Behind the water and isoprene preheating with gasification, enter beds from reactor head and react, phosphorus acid content is 50%～80% of a catalyzer total mass in the catalyzer, and boron content is 4%～9% of catalyzer total mass.In temperature of reaction is 180～300 ℃, and water and isoprene mol ratio are 4.0～8.0, and air speed LHSV is 0.1～0.5h
-1, reaction pressure is under the condition of normal pressure～0.3MPa, isoprene and water carry out addition and isomerization reaction, generate methyl isopropyl Ketone.
Described catalyzer is H
3PO
4-B/ diatomite.
Phosphorus acid content is preferably 60%～70% of catalyzer total mass in the described catalyzer.
Boron content is 5%～7% of catalyzer total mass in the described catalyzer.
Preferred 200～250 ℃ of described temperature of reaction.
Described water and isoprene mol ratio preferred 5.0～7.0.
The preferred 0.2MPa of described reaction pressure.
H
3PO
4-B/ diatomite catalyzer adopts blend-immersion process for preparing.With selected diatomite support and massfraction is 85% ortho-phosphoric acid and boric acid hybrid infusion by a certain percentage, again through moulding, drying, the roasting of matter homogenizing and catalyst precursor.After prepared catalyzer adds reactor, after activating under the moisture vapor atmosphere, just can be used for reaction.
By a large amount of experiments the catalyst surface deactivation mechanism is studied, be found that, at H
3PO
4The height of the quantity of the phosphoric acid that-B/ diatomite catalyst surface exists and composition decision catalyst activity, catalyst surface phosphoric acid mainly is made up of ortho-phosphoric acid, tetra-sodium and a small amount of Tripyrophosphoric acid, preceding two kinds of phosphoric acid can provide the middle and high intensity acid site of some amount, be the reactive activity position, and ortho-phosphoric acid and tetra-sodium are mainly derived from catalyst surface Si
3(PO
4)
4(P
2O
5/ SiO
2=0.75) and SiP
2O
7(P
2O
5/ SiO
2=1) hydrolysis.In the catalyzer use, by Si
3(PO
4)
4And SiP
2O
7The phosphoric acid that hydrolysis produces continues to run off from catalyst surface, not only can cause catalyst activity reduction, the more important thing is to cause caving in of catalyst backbone structure, causes the catalyzer argillization, makes catalyst bed stressor layer falling-rising height, has shortened the catalyzer life cycle.When with BPO
4After adding catalyzer, because BPO
4Have quite high stability, make the intensity of catalyzer and anti-argillization ability all be significantly improved.
The invention provides a kind of production method of methyl isopropyl Ketone.By at H
3PO
4Introduce boron in the/diatomite catalyzer, and generate the borophosphoric acid favourable, under the prerequisite that keeps catalyst activity, improved the stability of catalyzer effectively the rugged catalyst skeleton structure at catalyst surface.Compared with prior art, adopt H
3PO
4-B/ diatomite catalyzer is with existing H
3PO
4/ diatomite is compared, and obviously improve the work-ing life of catalyzer, and H has effectively drawn up
3PO
4The defective of easy loss of/diatomite catalyzer inherent phosphoric acid and the easy argillization of catalyzer makes catalyzer prolong life cycle, and has reduced the catalyzer cost of use significantly.
Embodiment
In an embodiment, the isoprene transformation efficiency is defined as:
[embodiment 1～6]
Hydration reactor is the stainless steel tubular type reactor of a φ 25mm * 1000mm, and reaction tubes loads the H that diameter is 5mm * 8mm respectively
3PO
4-B/ diatomite catalyzer 100 ml, reactor bottom filling inert ceramic balls.H in the catalyzer
3PO
4Content 50%～80%, boron content are 4～9%, and remainder is a carrier.
With water and isoprene gasify respectively mix after, be preheated to design temperature, enter H
3PO
4-B/ diatomite beds carries out hydration reaction.180～300 ℃ of temperature of reaction, water and isoprene mol ratio are 4.0～8.0, air speed LHSV is 0.1～0.5h
-1, reaction pressure is normal pressure～0.3MPa.Reaction pressure is regulated by the pressure controller of reactor exit.
[Comparative Examples]
In Comparative Examples, remove and use H instead
3PO
4Outside/diatomite the catalyzer, its hydrating process and condition and embodiment are identical.
The operational conditions of embodiment and Comparative Examples sees Table 1, the results are shown in Table 2:
Table 1:
| Temperature/℃ | Pressure/MPa | Water/isoprene mol ratio | Air speed/h -1 | The catalyzer phosphorus acid content/(%) | Catalyzer boron content/(%) | |
| Embodiment 1 | 180 | Normal pressure | 4.0 | 0.1 | 50 | 4.0 |
| Embodiment 2 | 200 | 0.1 | 5.0 | 0.2 | 60 | 5.0 |
| Embodiment 3 | 220 | 0.2 | 6.0 | 0.3 | 70 | 7.5 |
| Embodiment 4 | 250 | 0.3 | 7.0 | 0.4 | 80 | 9.0 |
| Embodiment 5 | 300 | 0.1 | 8.0 | 0.5 | 65 | 6.0 |
| Embodiment 6 | 220 | 0.2 | 6.2 | 0.33 | 65 | 6.0 |
| Comparative Examples | 220 | Normal pressure | 6.2 | 0.33 | 65 | 0 |
Table 2:
Claims (8)
1. the production method of methyl isopropyl Ketone.This method is with H
3PO
4-B/ diatomite is catalyzer, makes isoprene and water be converted into methyl isopropyl Ketone in adiabatic reactor.Behind the water and isoprene preheating with gasification, enter beds from reactor head and react, phosphorus acid content is 50%～80% of a catalyzer total mass in the catalyzer, and boron content is 4%～9% of catalyzer total mass.In temperature of reaction is 180～300 ℃, and water and isoprene mol ratio are 4.0～8.0, and air speed LHSV is 0.1～0.5h
-1, reaction pressure is under the condition of normal pressure～0.3MPa, isoprene and water generate methyl isopropyl Ketone through addition and isomerization reaction.
2. the production method of methyl isopropyl Ketone according to claim 1 is characterized in that, described catalyzer is H
3PO
4-B/ diatomite.
3. the production method of methyl isopropyl Ketone according to claim 1 is characterized in that, described hydration temperature is 180～300 ℃.
4. the production method of methyl isopropyl Ketone according to claim 1 is characterized in that, described water and isoprene mol ratio are 4.0～8.0.
5. the production method of methyl isopropyl Ketone according to claim 1 is characterized in that, described air speed is 0.1～0.5h
-1
6. the production method of methyl isopropyl Ketone according to claim 1 is characterized in that, described reaction pressure is normal pressure～0.3MPa.
7. the production method of methyl isopropyl Ketone according to claim 2 is characterized in that, H in the described catalyzer
3PO
4Add-on is 50%～80% of a catalyzer total mass.
8. the production method of methyl isopropyl Ketone according to claim 2 is characterized in that, the boron add-on is 4%～9% of a catalyzer total mass in the described catalyzer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006101174824A CN101168497A (en) | 2006-10-24 | 2006-10-24 | Method for producing methyl isopropyl ketone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006101174824A CN101168497A (en) | 2006-10-24 | 2006-10-24 | Method for producing methyl isopropyl ketone |
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| Publication Number | Publication Date |
|---|---|
| CN101168497A true CN101168497A (en) | 2008-04-30 |
Family
ID=39389286
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|---|---|---|---|
| CNA2006101174824A Pending CN101168497A (en) | 2006-10-24 | 2006-10-24 | Method for producing methyl isopropyl ketone |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651252A (en) * | 2019-01-11 | 2019-04-19 | 中化农业（临沂）研发中心有限公司 | The method for preparing 3,4- dimethyl pyrazole and its phosphate and metal organic complex |
| CN112745207A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Method for producing MIBK (methyl isobutyl ketone) by acetone one-step method |
| CN113443975A (en) * | 2021-06-28 | 2021-09-28 | 阿拉善经济开发区新鑫化工有限责任公司 | Method for producing methyl isopropyl ketone under pressure and application |
-
2006
- 2006-10-24 CN CNA2006101174824A patent/CN101168497A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651252A (en) * | 2019-01-11 | 2019-04-19 | 中化农业（临沂）研发中心有限公司 | The method for preparing 3,4- dimethyl pyrazole and its phosphate and metal organic complex |
| CN112745207A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Method for producing MIBK (methyl isobutyl ketone) by acetone one-step method |
| CN112745207B (en) * | 2019-10-31 | 2022-08-12 | 中国石油化工股份有限公司 | Method for producing methyl isobutyl ketone by acetone one-step method |
| CN113443975A (en) * | 2021-06-28 | 2021-09-28 | 阿拉善经济开发区新鑫化工有限责任公司 | Method for producing methyl isopropyl ketone under pressure and application |
| CN113443975B (en) * | 2021-06-28 | 2023-09-26 | 阿拉善经济开发区新鑫化工有限责任公司 | Method for producing methyl isopropyl ketone under pressure and application thereof |
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Open date: 20080430 |