CN1508108A - Combined process for synthesizing amylene alcohol - Google Patents
Combined process for synthesizing amylene alcohol Download PDFInfo
- Publication number
- CN1508108A CN1508108A CNA021564515A CN02156451A CN1508108A CN 1508108 A CN1508108 A CN 1508108A CN A021564515 A CNA021564515 A CN A021564515A CN 02156451 A CN02156451 A CN 02156451A CN 1508108 A CN1508108 A CN 1508108A
- Authority
- CN
- China
- Prior art keywords
- reaction
- isopentene
- preferred
- amyl alcohol
- tertiary amyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The method for synthesizing tertiary amyl alcohol by adopting combination process uses the heavy diesel oil of refinery as raw material and comprises the following steps: using zeolite catalyst with MFI structure to make shape selective cracking to obtain the light hydrocarbon component with high-concentration cavity isopentene, using said component as raw material for synthesizing tertiary amyl alcohol, mixing it with deionized water and small quantity of solvent, feeding them into the fixed bed reactor with solid super acid and cationic resin combined catalyst to make hydration reaction, and the subsequent step is the conventional separation process. Its activity isopentene conversion rate is high, and the yield of tertiary amyl alcohol is high.
Description
The present invention relates to the novel process that a kind of tertiary amyl alcohol is produced, different with prior art, it is raw material that system adopts the heavy gas oil of refinery, zeolite catalyst through having the MFI structure carries out shape slective cracking, produces to have the i.e. light hydrocarbon component of 2 methyl butenes-1 and 2 methyl butenes-2 (2M1B+2M2B) of the active isopentene of high density.This component is mixed with deionized water and a small amount of solvent as the raw material of synthetic tertiary amyl alcohol, enters the fixed-bed reactor that solid super-strong acid and resin cation (R.C.) combination catalyst are housed, and carries out hydration reaction, and follow-up is conventional separation process.
Tertiary amyl alcohol is a kind of basic Organic Chemicals, is mainly used in to produce novel agrochemical pinacolone, triazolone etc.Tertiary amyl alcohol also is the raw material of synthetic perfume, color film coupler; And can be in order to produce softening agent, non-ferrous metal flotation agent and paint solvent etc.Also can be used as lubricating oil, hydraulic efficiency oil and other fortifying of petroleum products.In addition, tertiary amyl alcohol still is the raw material of synthetic resins perforating agent.At cellulose ester, ether of cellulose; Production fields such as solubility promoter that the solvent of dope, varnish, nitro spray paint and spices, mineral flotation agent, oxidation inhibitor are the widespread use tertiary amyl alcohol also.
At present, the industrial traditional acetone-acetylene method of all adopting is produced tertiary amyl alcohol, and this technological process is to be raw material with acetone, acetylene, generates methyl butine ketone through catalyzed reaction, obtains tertiary amyl alcohol through hydrogenation again.This raw materials technology cost height, the technical process complexity; Also can produce industrial residue during with calcium carbide hydrolysis system acetylene, environment is polluted.
Active isopentene and water synthetic tertiary amyl alcohol under the effect of catalyzer is a known technology, comprise U.S. Pat 3,257,469, propose to use polar organic solvent, the mutual solubility that increases isopentene and water improves the method for hydration reaction transformation efficiency, but owing to use lower boiling alcohol, ketone and ethers to make solvent, make the back separation system complicated, energy consumption is bigger.US4,182,920 propose three grades of hydration reaction modes, and the flow process required equipment is more, the process operation complexity.US4,960,961 propose a kind of method without solvent, and near the scope the isopentene boiling point is carried out hydration reaction, and still the required reaction times reaches 90～236 hours, and Practical significance is little.Chinese patent CN1233609A proposes to be higher than with boiling point polar organic solvent such as isopropylcarbinol, propyl carbinol, butyleneglycol and the diacetone alcohol etc. of tertiary amyl alcohol, wherein preferred propyl carbinol and Pentyl alcohol.But it is excessive to invent used solvent ratios, and not only energy consumption is returned subsequent separation system greatly and brought difficulty.Another Chinese patent CN1374284A deviates from conjugated dienes impurity wherein when proposing catalytic distillation separation of C 5 cuts, carry out hydration reaction then.This invention is the MIO at the technology of harshness such as catalytic cracking FCC and voluminous isomeric olefine, and the C 5 fraction of its gasoline just is suitable for as the hydration raw material.To demulcent technology, because C 5 fraction does not almost have conjugated dienes impurity, so do not need the catalytic distillation combination process.The selected hydration raw material of prior art is fluid catalytic cracking, steam cracking system ethene and third, the superimposed C 5 fraction of butylene, and the content of active isopentene is lower, generally 25～40%; Transformation efficiency is not high in addition, so the yield of purpose product tertiary amyl alcohol is low.In addition, prior art is employed all to be the cation resin catalyzing agent, because the restriction of H+ exchange capacity, improving activity of such catalysts also has certain difficulty.
The present invention has overcome the deficiencies in the prior art, and its characteristics are as follows:
1. proposing a new raw material route promptly adopts the heavy gas oil of refinery to comprise: direct-distilled normal pressure three, four line distillates, decompression cat head and decompression one line distillate, catalytic cracking heavy gas oil.The boiling range scope of this heavy gas oil is at 150～400 ℃, 20～35 ℃ of condensation points, and total nitrogen content is less than 200 μ g/g, and the alkali nitrogen content is less than 100 μ g/g.
2. heavy gas oil shape slective cracking reaction conditions relaxes, and catalyst system therefor is a kind of zeolite catalyst with MFI structure, is HZSM-5 specifically.The lighter hydrocarbons C 5 fraction that the reaction of heavy gas oil shape slective cracking is produced is as the raw material of hydration tertiary amyl alcohol, and the massfraction of its active isopentene (2M1B+2M2B) is greater than 50%.
3. the C5 light hydrocarbon component of producing through the demulcent shape slective cracking has only the conjugated dienes impurity of trace, and its content need not design special equipment in addition and deviate from impurity less than 10 μ g/g.
4. hydration reaction is used solid super-strong acid and resin cation (R.C.) combination catalyst, has improved the transformation efficiency and the selectivity of active isopentene hydration reaction.Prior art is used resin catalyst merely, and the transformation efficiency of isopentene is usually less than 48%, and transformation efficiency of the present invention is greater than 50%.
5. because the active isopentene concentration of raw material of the present invention transformation efficiency height, selectivity high and catalyzer is good, obviously improved the yield of combination process purpose product tertiary amyl alcohol.
6. to have selected a kind of novel solvent unlike the prior art for use be ethylene glycol to combination process, solvent ratio reduced more than 30%, the corresponding minimizing of the energy consumption of process.
The combination process flow process is seen accompanying drawing, and technical process specifically describes as follows:
Heavy gas oil is from raw material tank field feeder, incoming stock oily surge tank is extracted out through feedstock pump, through interchanger and from the material heat exchange at the bottom of the separation column, enter process furnace again and be heated to temperature of reaction, enter reactor then, carry out the selective cracking reaction under the effect of catalyzer, reaction product enters the product separation column and carries out product separation.Ejecting the reacted gas that comes from separation column but enters the fractionation return tank of top of the tower with gasoline through cat head oil gas air cooler and separates.The rich gas of telling from tank deck is after pneumatic press compression cooling, and isolated liquefied gas goes out device as a kind of byproduct.Raw gasline is extracted out through the raw gasline pump, and a part is made the fractionation trim the top of column, and another part is as the raw material of separation of C 5 lighter hydrocarbons.Low-coagulation diesel oil is extracted out from oil header, through the stripping tower stripping, and is cooled with circulating water the back carrying device, makes the solar oil blend component.Raw gasline after the heat exchange obtains qualified C 5 fraction through debutanizing tower and dehexanizing column.The C that obtains by the heavy gas oil shape slective cracking
5Cut, separate Buddhist such as C by hydrated product
5The water that the tower quantizer returns, the deionized water that replenishes by the charging proportioning of processing requirement, three strands of materials converge and are pumped to 0.75Mpa; The ethylene glycol that is returned by finishing column is pumped to 0.8Mpa and converges with last strand of material after cooling off, and enters reactor through static mixer again.Temperature with the water cooler controlling reactor inlet feed on the pipeline.Reactor is a fixed-bed type, and the isopentene in the material becomes tertiary amyl alcohol with hydration.The material that reactor comes out enters the rectifying tower middle part.C
5Tower is a corrugated-plate packed tower, with the steam indirect heating.The material steam that is come out by cat head becomes liquid through condenser condenses, is divided into two liquid layers in quantizer: the upper strata is C
5Hydrocarbon, partial reflux is gone into top of tower, and part is drawn out-of-bounds; Lower floor is a water, all Returning reactor.It is anhydrous tertiary amyl alcohol, ethylene glycol mixture that tower bottom is drawn material, sends into the finishing column middle part.Finishing column also is a corrugated-plate packed tower, with the steam indirect heating.The material steam that is come out by cat head is the finished product tertiary amyl alcohol through condenser condenses, and a part passes back into top of tower, and a part is drawn as finished product.Tower bottom is drawn ethylene glycol, sends reactor back to.In long-term the driving, a small amount of high-boiling-point impurity that reaction produces can accumulate in the round-robin ethylene glycol, at this moment tells a small gangs of material in the propyl carbinol by Returning reactor and sends in the weight-removing column and purify.Weight-removing column also is a ripple packing, carries out operate continuously.The ethylene glycol that overhead fraction purifies, Returning reactor, bottom product position heavy seeds is sent out-of-bounds.
The processing condition of heavy gas oil shape slective cracking and C 5 fraction hydration reaction:
The shape slective cracking temperature of reaction: 300～420 ℃, preferred 360～400 ℃; Reaction pressure: 0.05～1.0MPa (gauge pressure), preferred 0.05～0.5MPa (gauge pressure); Reaction velocity: 0.5～3.0h
-1, preferred 1.0～2.0h
-1
C 5 fraction hydration reaction temperature: 40～80 ℃, preferred 60～70 ℃; Reaction pressure: 0.5～1.0Mpa (gauge pressure), preferred 0.6～0.8MPa (gauge pressure); Reaction velocity: 0.5～3.0h
-1, preferred 1.0～2.0h
-1Water/oil (C
5Cut): 0.1～0.5 (mass ratio, down together), preferred 0.2～0.3; Solvent/oil: 1.0～5.0, preferred 1.5～2.0.
Below by embodiment and Comparative Examples, the invention will be further described, but the present invention is not limited to this.Said active isopentene with water generation electrophilic addition reaction, generates tertiary amyl alcohol among the embodiment under the effect of an acidic catalyst.Hydration raw material, product purity and solvent be by gas chromatograph for determination, hydrogen flame ionization detector, and chromatographic column is an OV-01 quartz elastic capillary tube post.The chromatographic instrument operational condition is: 230 ℃ of vaporizing chambers, and 250 ℃ of detectors, initial 30 ℃ of post oven temperature, degree stops 15min, 2 ℃/min of temperature rise rate, temperature is 100 ℃ eventually, stops 35min.
Isopentene transformation efficiency X
IC5=, tertiary amyl alcohol selectivity S
IC5OHAnd tertiary amyl alcohol is to the yield Y of C 5 fraction
IC5OHClicking formula calculates:
X
iC5＝＝(iC
5 ＝ Rin-iC
5 ＝ Rout/iC
5 ＝ Rin)×100％
S
iC5OH＝{(iC
5OH
Rout/88)/[(iC
5 ＝ Rin-iC
5 ＝ Rout)/70}×100％
Y
iC5OH＝F
C5×C
iC5＝×X
iC5＝×S
iC5OH
In the formula: iC
5 = RinBe reactor inlet isopentene concentration, massfraction %;
IC
5 = RoutBe reactor outlet isopentene concentration, massfraction %;
IC
5OH
RoutBe reactor outlet primary isoamyl alcohol concentration, massfraction %;
F
C5For the C 5 fraction feed rate, by 100g/h;
C
IC5=Be isopentene concentration in the C 5 fraction, massfraction %;
Embodiment 1
Present embodiment is raw material with heavy gas oil, by the active isopentene of shape slective cracking prepared in reaction.Heavy gas oil is normal two, the vacuum 1st side cut mixed fraction oil that LIAOHE CRUDE distillation obtains, 178～385 ℃ of its flow process scopes, condensation point+29C, existent gum 40mg/ml, total nitrogen content 186 μ g/g, alkali nitrogen content 94 μ g/g.In fixed-bed reactor, the HZSM-5 catalyzer 100g that packs into, the commercial trade mark of catalyzer is CTL-1, its bulk density 0.645g/ml, crushing strength 13kg/cm, efflorescence degree 0.01%, physical dimension φ 1.8 * 2～5mm.Fixed-bed reactor are that φ 39 * 1000mm gapless stainless steel tube is made.With silicon controlled rectifier temperature control system control reaction temperature.The temperature of reaction of shape slective cracking reaction test is that 360 ℃, reaction pressure are 0.05MPa (gauge pressure), reaction velocity 1.0h
-1Reaction product is through fractionation, and the by product gasoline of gained is further distillation again, is the raw material of hydration reaction from the effusive C 5 fraction of cat head, and its character is listed table 1 in.
Table 1 C 5 fraction character and composition
Project boiling point ℃ composition m%
C
4 1.000
3M1B 20.2 0.686
iC
5 0 27.9 4.720
nC
5 = -1 30.0 2.129
2M1B 31.2 13.163
iC
5 ＝ 34.1 0.000
nC
5 0 36.1 17.571
tC
5 ＝-2 36.4 10.923
cC
5 ＝-2 37.0 5.425
2M2B 38.6 43.383
1，3-rC
5 ＝ 41.0 0.000
1，3-C
5 ＝ 42.1 0.000
rC
5 ＝ 44.3 0.000
C
6 + 1.000
2M1B+2M2B 56.546
Trace impurity μ g/g
Mercaptan sulfur 17
Total sulfur 25
Alkali nitrogen 1.3
Total nitrogen 4.0
Metal ion 0.8
Embodiment 2
Present embodiment is a raw material with the C 5 fraction that the reaction of embodiment 1 heavy gas oil shape slective cracking generates, and investigates the effect of hydration reaction.Make the fixed-bed reactor in the use-case 1, at the middle part of reactor filling solid super acids and macropore strong acid cation resin, the mass ratio of its compatibility is 1: 5, and total amount is 100g.Solid super-strong acid is self-control SO
4 2-/ ZrO
2, the macroporous strong-acid cation resin is commercially available S-54
#Resin.Reaction mass is divided into two strands, and one is a C 5 fraction oil, and another strand is deionized water and ethylene glycol mixture, and the mass ratio of solvent and active isopentene is 2.0, and the mass ratio of deionized water and active isopentene is 1.25.In above ratio metering, two strands of materials pump into fixed-bed reactor through the small-sized static mixing tank.65 ℃ of control reaction temperature, reaction pressure 0.6MPa, reaction velocity 1.0h
-1From back pressure valve outlet sampling analysis, the isopentene transformation efficiency that records is 56.6% after the stable reaction conditions, and selectivity is 98.8%, and tertiary amyl alcohol is 31.62% to the yield of C 5 fraction.
Comparative Examples 1
Comparative Examples 1 is in order to investigate the influence of different material to hydration reaction.Catalyzer that is loaded in the reactor and test operation condition are identical with embodiment 2, difference be the C 5 fraction of the catalytic cracking FCC that only is to use as the hydration reaction raw material, the content of its active isopentene is 25%.The isopentene transformation efficiency that reaction records is 50.7%, and selectivity is 98.6%, and tertiary amyl alcohol is 12.50% to the yield of C 5 fraction.
Comparative Examples 2
Comparative Examples 2 is in order to investigate the influence of different catalysts to hydration reaction.Raw material and test operation that Comparative Examples 2 is used are identical with embodiment 2, and the catalyzer that difference is in the reactor and is adorned is the S-54 of 100g
#Resin.The isopentene transformation efficiency that reaction records is 46.7%, and selectivity is 98.2%, and tertiary amyl alcohol is 25.93% to the yield of C 5 fraction.
Comparative Examples 3
Comparative Examples 3 is in order to investigate the influence of different solvents to hydration reaction.The catalyzer of being adorned in raw material, test operation and the reactor that Comparative Examples 3 is used is identical with embodiment 1, and difference is that the solvent of selecting for use is a propyl carbinol.The mass ratio of solvent and active isopentene is 5.0, and the isopentene transformation efficiency that reaction records is 46.2%, and selectivity is 98.6%, and tertiary amyl alcohol is 25.76% to the yield of C 5 fraction.
Embodiment 3
Present embodiment is in order to investigate solid super-strong acid and macropore strong acid cation mixed with resin activity of such catalysts stability.The catalyzer of being adorned in raw materials used, solvent, test operation and the reactor is identical with embodiment 1.Test continuous operation 1000h, temperature of reaction, pressure and air speed remain unchanged all the time, isopentene transformation efficiency 56.0～58.0%, selectivity 98.0～99.0%, tertiary amyl alcohol is 32.0～34.0% to the yield of C 5 fraction.Embodiment 3 explanation combination catalyst and technological operation good stabilities, but industrial implementation long-term operation.
Embodiment 4
Present embodiment is for the product purity of investigating hydration reaction and yield.With the reaction product of embodiment 3 accumulative total C 5 fraction charging 10kg gained, small-sized packed column distillation is isolated unreacted C 5 fraction through the laboratory; The redistillation after the extraction dehydration of unreacted deionized water, product tertiary amyl alcohol and solvent ethylene glycol separates tertiary amyl alcohol and solvent ethylene glycol, obtains the tertiary amyl alcohol 3.2kg of 99.5% purity from cat head.
Claims (12)
1. the method for the synthetic tertiary amyl alcohol of a combination process is characterized in that adopting the raw material route of refinery heavy gas oil, by the shape slective cracking catalyzed reaction, produces the light hydrocarbon component with the active isopentene of high density, as the raw material of synthetic tertiary amyl alcohol.
2. according to right 1 described method, it is characterized in that refinery heavy gas oil comprises: direct-distilled normal pressure three, four line distillates, decompression cat head and decompression one line distillate, catalytic cracking heavy gas oil.
3. according to right 1 and 2 described methods, the boiling range scope that it is characterized in that heavy gas oil is at 150～400 ℃, 20～35 ℃ of condensation points, and total nitrogen content is less than 200 μ g/g, and the alkali nitrogen content is less than 100 μ g/g.
4. according to right 1～3 described method, it is characterized in that the used catalyzer of heavy gas oil shape slective cracking reaction is a kind of zeolite catalyst of the MFI of having structure.
5. according to right 1～4 described method, it is characterized in that the light hydrocarbon component that the reaction of heavy gas oil shape slective cracking is produced, as the raw material of synthetic tertiary amyl alcohol, the active isopentene of high density is arranged, its massfraction is greater than 50%.
6. according to right 1～5 described method, it is characterized in that raw material as synthetic tertiary amyl alcohol, the active isopentene light hydrocarbon component of high density mixes with deionized water and a small amount of solvent, enters the fixed-bed reactor that solid super-strong acid and resin cation (R.C.) combination catalyst are housed, and carries out hydration reaction.
7. according to right 6 described methods, it is characterized in that the employed solid super acid catalyst of hydration reaction is SO
4 2-/ M
xO
yThe type super-strong acid catalytic material.With the solid super acid catalyst compatibility be the macropore strong acid cation resin.
8. according to right 7 described methods, its feature in the strength of acid of solid super acid catalyst greater than 100% the vitriol oil; The exchange capacity of macropore strong acid cation resin is greater than 4.5mmgH
+/ g.The ratio of solid super-strong acid and macropore strong acid cation resin compatibility is 1: 1～1: 10, preferred 1: 5.
9. according to right 6 described methods, it is characterized in that the employed solvent of hydration reaction is an ethylene glycol, the mass ratio of solvent and active isopentene is 1.0～5.0, preferred 2.0～3.0.
10. according to right 6 described methods, it is characterized in that the employed water of hydration reaction is deionized water, its specific conductivity is less than 10 μ s/cm.The mass ratio of deionized water and active isopentene is 0.5～3.0, preferred 1.2～1.3.
11. according to right 4 described methods, the condition that its feature is reacted at the heavy gas oil shape slective cracking: 260～420 ℃ of temperature of reaction, preferred 300～400 ℃; Reaction pressure 0.1～0.8MPa, preferred 0.2～0.4MPa; Reaction velocity 0.5～2.0h
-1, preferred 0.8～1.0h
-1
12. according to right 5 described methods, its feature is in the condition of hydration reaction: 20～80 ℃ of temperature of reaction, preferred 50～70 ℃; Reaction pressure 0.1～1.0MPa, preferred 0.4～0.8MPa; Reaction velocity 0.3～2.0h
-1, preferred 0.6～1.0h
-1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA021564515A CN1508108A (en) | 2002-12-16 | 2002-12-16 | Combined process for synthesizing amylene alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA021564515A CN1508108A (en) | 2002-12-16 | 2002-12-16 | Combined process for synthesizing amylene alcohol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1508108A true CN1508108A (en) | 2004-06-30 |
Family
ID=34236220
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA021564515A Pending CN1508108A (en) | 2002-12-16 | 2002-12-16 | Combined process for synthesizing amylene alcohol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1508108A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304362A (en) * | 2012-03-13 | 2013-09-18 | 上海博润石化科技发展有限公司 | Preparation method of high purity cyclopentene |
| CN107879894A (en) * | 2016-09-29 | 2018-04-06 | 中国石油化工股份有限公司 | A kind of preparation method of tert-pentyl alcohol |
| CN110050055A (en) * | 2017-11-15 | 2019-07-23 | 巴西石油公司 | Obtain method, renewable hydrocarbon stream and the gasoline preparaton for being suitable as the renewable hydrocarbon stream of gasoline preparaton component |
| CN110172013A (en) * | 2019-06-24 | 2019-08-27 | 中国石油化工股份有限公司 | A kind of technique based on catalytic distillation solvent method synthesis tert-pentyl alcohol |
-
2002
- 2002-12-16 CN CNA021564515A patent/CN1508108A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304362A (en) * | 2012-03-13 | 2013-09-18 | 上海博润石化科技发展有限公司 | Preparation method of high purity cyclopentene |
| CN107879894A (en) * | 2016-09-29 | 2018-04-06 | 中国石油化工股份有限公司 | A kind of preparation method of tert-pentyl alcohol |
| CN110050055A (en) * | 2017-11-15 | 2019-07-23 | 巴西石油公司 | Obtain method, renewable hydrocarbon stream and the gasoline preparaton for being suitable as the renewable hydrocarbon stream of gasoline preparaton component |
| CN110172013A (en) * | 2019-06-24 | 2019-08-27 | 中国石油化工股份有限公司 | A kind of technique based on catalytic distillation solvent method synthesis tert-pentyl alcohol |
| CN110172013B (en) * | 2019-06-24 | 2023-06-16 | 中国石油化工股份有限公司 | Process for synthesizing tertiary amyl alcohol based on catalytic distillation solvent method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101343652B1 (en) | 1- 2- 4 50% process for preparation of polyisobutylene whose content of terminal double bonds is more than 50% from an industrial c4 hydrocarbon stream comprising 1-butene 2-butene and isobutene | |
| CN101497548B (en) | Method for producing n-butene-oligomers and 1-butene from mixture-I made of hydrocarbons having four carbon atoms | |
| CN101475429B (en) | Method for comprehensive utilization of cracking C4 | |
| TW200418777A (en) | Preparation of highly pure methyl tert-butyl ether | |
| CN106854139B (en) | Method for preparing tert-butylphenol by using phenol-containing tar | |
| CN102633588B (en) | Method for preparing high-purity isobutene from raffinate C4 by means of separation | |
| CN202081036U (en) | Mixed gas separating system in MTP reaction | |
| JP2017526779A (en) | Method for producing polybutene | |
| CN1148337C (en) | Process for preparing isopentene containing high content of 2-methyl-2-butene from methyl tertiary amyl ether | |
| CN101260016A (en) | Refining device for preparing high-pure isobutene by cracking methyl tertiary butyl ether and technique thereof | |
| CN101245255B (en) | Etherification method for producing clean gasoline | |
| CN103619785A (en) | Method for producing diisobutylene starting from mixed C4 fraction | |
| CN102050690B (en) | Isoolefine production method | |
| CN102603452A (en) | Method for preparing isoalkenes through isomerizing linear alkenes | |
| CN110172013B (en) | Process for synthesizing tertiary amyl alcohol based on catalytic distillation solvent method | |
| CN1508108A (en) | Combined process for synthesizing amylene alcohol | |
| CN102070390B (en) | The method of refinery's mixed c 4 propylene | |
| CN111018644B (en) | Method for improving comprehensive utilization value of mixed C4 | |
| CN1374934A (en) | Oligomerization of olefins | |
| CN102492466A (en) | Process and device for producing catalytic gasoline by etherifying | |
| CN1239444C (en) | Isoalkene producing process | |
| CN114349603A (en) | Method for preparing cyclopentanol from cyclopentyl acetate | |
| CN1374284A (en) | Production process of tert-amyl alcohol | |
| CN1050311C (en) | Method for producing high-purity butene-1 | |
| CN1065656A (en) | The preparation of diglycol monotertiary butyl ether |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C57 | Notification of unclear or unknown address | ||
| DD01 | Delivery of document by public notice |
Addressee: Beijing Meitong Technology Development Co.,Ltd. Document name: Notice of qualification for supplementary trial |
|
| C06 | Publication | ||
| PB01 | Publication | ||
| C57 | Notification of unclear or unknown address | ||
| DD01 | Delivery of document by public notice |
Addressee: Sun Jianjun Document name: Notification before expiration of term |
|
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |