CN104230856B - The production method of butylene oxide ring - Google Patents
The production method of butylene oxide ring Download PDFInfo
- Publication number
- CN104230856B CN104230856B CN201310237302.6A CN201310237302A CN104230856B CN 104230856 B CN104230856 B CN 104230856B CN 201310237302 A CN201310237302 A CN 201310237302A CN 104230856 B CN104230856 B CN 104230856B
- Authority
- CN
- China
- Prior art keywords
- hydrogen phosphide
- oxide ring
- butylene oxide
- phosphide cumene
- butylene
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Epoxy Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to the production method of a kind of butylene oxide ring, mainly solving prior art, to there is butylene oxide ring selectivity low, the problem that catalyzer work-ing life is short. The present invention comprises step by adopting: a) synthesize hydrogen peroxide cumene oxidation liquid; B) controlling organic acid weight percentage in hydrogen phosphide cumene oxidation solution and be not more than 0.3%, the weight percentage of basic metal or alkaline-earth metal ions is not more than 0.1%, and the weight percentage of water is not more than 0.5%; C) hydrogen phosphide cumene oxidation solution and butylene are under the effect of catalyzer, and under liquid-phase condition, reaction generates butylene oxide ring and alpha, alpha-dimethyl benzyl alcohol; D) alpha, alpha-dimethyl benzyl alcohol generates isopropyl benzene with hydrogen generation hydrogenolysis in the presence of a catalyst; The isopropyl benzene generated is circulated to the technical scheme of step a) as the raw material preparing hydrogen phosphide cumene, solves this problem preferably, can be used for preparing in the industrial production of butylene oxide ring.
Description
Technical field
The present invention relates to the production method of a kind of butylene oxide ring.
Background technology
Polyether glycol, is called for short polyethers, is the novel synthetic lubricant base oil end of the seventies in last century, the beginning of the eighties researching and developing out, and its kind is a lot, mainly distinguishes with monomer. What the monomer of synthesizing polyether had been developed at present has oxyethane, propylene oxide, butylene oxide ring and tetrahydrofuran (THF) etc. Polyethers is except as except the base oil of novel ucon oil, can being also the important source material producing urethane, and have the multiple functions such as bubble, breakdown of emulsion, dispersion, infiltration, emulsification that disappear. Due to the restriction by butylene oxide ring production technology, our common polyethers is mainly taking oxyethane or propylene oxide as the polyether glycol synthesized by raw material monomer at present, it is less taking butylene oxide ring to be that the polyethers synthesized by monomer accounts for the market share, but due to himself characteristic, the solubleness of butylene oxide ring polymkeric substance in water is lower than the polyethylene oxide of same chain segment length and poly(propylene oxide), its purposes is constantly widened, and has vast potential for future development.
Except generating except polyethers, similar with propylene oxide with oxyethane, butylene oxide ring is also very active, can with the compound containing active hydrogen atom, as water, alcohol class, polyvalent alcohol, phenols, mercaptan, ammonia, amine class, sour class etc. are reacted.The butyleneglycol that butylene oxide ring generates through hydration, can be used for manufacturing softening agent, and the amino butanol of the alcohol ether that butylene oxide ring and ethanol synthesis generate and ammonia synthesis, for coatings industry. The reactant of 1,2-butylene oxide ring, 2,3-butylene oxide ring, ring oxygen Trimethylmethane and boric acid, can be used for mineral oil, hydraulic pressure oil additives and sterilant, wood preservative. The segmented copolymer of butylene oxide ring and oxyethane is for the production of the tensio-active agent such as nonionic emulsifier, emulsion splitter. Butylene oxide ring also can be used as the special efficacy acid scavenger of the chlorinated hydrocarbon solvents such as trieline, and also there is extensive use this aspect such as external medicine and chemistry of pesticide product.
At present, the production of butylene oxide ring mainly adopts chlorohydrination, and this method is seriously polluted, consumption indicators height, poor product quality. In order to decreasing pollution, reducing material consumption and energy consumption, the emphasis of research is at present, in the presence of a catalyst, taking C4 alkene as raw material, adopts peroxide oxidant, butylene is converted into butylene oxide ring.
China petrochemical industry Beijing Chemical Research Institute have studied make catalyzer with TS-1 HTS, with 30%H2O2For the 1-butylene catalytic epoxidation of oxygenant, under certain reaction conditions, butylene oxide ring selectivity 91% and H2O2Transformation efficiency 72%.
Document JP2001151764A proposes the technique that C4 conversion of olefines is epoxide, adopts Mo compound and boric acid ester to be catalyzer, and taking peroxidation Trimethylmethane as oxygenant, peroxidation Trimethylmethane transformation efficiency is 96.2%, and the selectivity of butylene oxide ring is 93.2%.
Lanzhou University develops Au/TiO2With TS-1 composite catalyst, taking oxygen as oxygenant, CO, for sacrificing reductive agent, can carry out 1-butylene epoxidation reaction [JiangJ at 0.48MPa and 40 DEG C; KungHH; KungMCetal, GoldBulletin (London, UnitedKingdom) (2009), 42 (4), 280-287].
Document CN201110290123.X discloses the production method of a kind of butylene oxide ring, and under oxidation reaction condition, by butylene and oxidising agent, described oxygenant is the gas containing ozone, and the selectivity of butylene oxide ring is between 68 ~ 89%.
In a word, it is low to there is butylene oxide ring selectivity in prior art, the problem that catalyzer work-ing life is short.
Summary of the invention
It is low that technical problem to be solved by this invention is that prior art exists butylene oxide ring selectivity, the problem that catalyzer work-ing life is short, it is provided that the production method of a kind of new butylene oxide ring. The method has catalyst activity height, good stability, butylene oxide ring selectivity height, environmental protection and the feature without joint product.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: the production method of a kind of butylene oxide ring, comprises the following steps:
A) isopropyl benzene and air generation peroxidation, obtain hydrogen phosphide cumene oxidation solution;
B) de-except the organic acid in hydrogen phosphide cumene oxidation solution, basic metal or alkaline-earth metal ions, Yi Jishui so that it is in organic acid weight percentage be not more than 0.3%, the weight percentage of basic metal or alkaline-earth metal ions is not more than 0.1%, and the weight percentage of water is not more than 0.5%;
C) through hydrogen phosphide cumene oxidation solution and the butylene of step b) process under the effect of catalyzer, reaction generation butylene oxide ring and alpha, alpha-dimethyl benzyl alcohol under liquid-phase condition;
D) alpha, alpha-dimethyl benzyl alcohol generates isopropyl benzene with hydrogen generation hydrogenolysis in the presence of a catalyst; The isopropyl benzene generated is circulated to step a) as the raw material preparing hydrogen phosphide cumene.
In technique scheme, it may be preferred that the reaction conditions of step a) is: temperature of reaction 0 ~ 200 DEG C, reaction pressure 0.1 ~ 5.0MPa.
In technique scheme, it may be preferred that in control hydrogen phosphide cumene oxidation solution, organic acid weight percentage is not more than 0.1%, and the weight percentage of basic metal or alkaline-earth metal ions is not more than 500ppm, and the weight percentage of water is not more than 0.2%. More preferably, in control hydrogen phosphide cumene oxidation solution, organic acid weight percentage is not more than 600ppm, and the weight percentage of basic metal or alkaline-earth metal ions is not more than 200ppm, and the weight percentage of water is not more than 0.1%.
In technique scheme, it may be preferred that at least one that described organic acid is selected from formic acid, acetic acid, propionic acid, oxalic acid, propanedioic acid, lactic acid or phenol.
In technique scheme, it may be preferred that described butylene is selected from butene-1, butylene-2 or iso-butylene, its corresponding epoxidation product is respectively 1,2-butylene oxide ring, 2,3-butylene oxide ring or 2-methyl isophthalic acid, 2-propylene oxide.
In technique scheme, it may be preferred that step c) reaction conditions is: temperature of reaction 25��160 DEG C, the mol ratio 1��20 of reaction pressure 0.1��10MPa, butylene and hydrogen phosphide cumene, the weight space velocity of hydrogen phosphide cumene 0.05��20 hour-1. More preferably, temperature of reaction is 40��130 DEG C, and reaction pressure is the mol ratio of 0.5��8.0MPa, butylene and hydrogen phosphide cumene is 2��15, and the weight space velocity of hydrogen phosphide cumene is 0.1��15 hour-1��
In technique scheme, it may be preferred that step c) catalyzer used is titanium-containing meso-porous or macroporous silica catalytic material Ti-HMS, Ti-MCM-41, Ti-TUD-1, Ti-SBA-15, Ti-KIT-1 or Ti-SiO2
In technique scheme, it may be preferred that the reaction conditions of step d) is: temperature of reaction 80 ~ 400 DEG C, reaction pressure 0.1 ~ 6.0MPa.
In technique scheme, it may be preferred that in described hydrogen phosphide cumene oxidation solution, the concentration expressed in percentage by weight of hydrogen phosphide cumene is 1 ~ 90%. More preferably, in described hydrogen phosphide cumene oxidation solution, the concentration expressed in percentage by weight of hydrogen phosphide cumene is 10 ~ 85%.
In the inventive method, step a) is oxidation step, adopts molecular oxygen that cumene oxidation is become hydrogen phosphide cumene, and this is a classical free radical reaction. Molecular oxygen used both can be that air can also adopt oxygen-rich air. This reaction both can carry out under the existence of catalyzer or additive, it is also possible to when efficiently carrying out without when any catalyzer or additive. Used catalyst or additive are generally basic metal, alkaline-earth metal, the oxyhydroxide of ammonia or carbonate, but consider from the aftertreatment angle of oxidation solution, preferential adopt air-oxidation system containing any additive. Under normal circumstances, the temperature of reaction of oxidation step and pressure are preferably 50 ~ 200 DEG C and 0.1 ~ 2MPa respectively. Temperature is too low, and reaction efficiency is low, maybe cannot carry out; Too high temperature then easily causes hydrogen phosphide cumene decompose or produce other by product.
In the inventive method, step b) is depickling, dealkalize metal or alkaline-earth metal ions and decompression concentrate step. Wherein depickling is the organic acid in the de-hydrogen phosphide cumene oxidation solution except producing in oxidation step. In oxidation step, along with the carrying out of reaction, the organic acid of some small molecules can be produced, such as formic acid, acetic acid, propionic acid, oxalic acid, propanedioic acid, lactic acid or phenol etc. Organic acid both can adopt organic solvent extraction technology to carry out de-removing, it is also possible to adopts basic metal, alkaline-earth metal or the oxyhydroxide of ammonia or the aqueous solution of carbonate to carry out washing de-except (being generally NaCO3Or the NaOH aqueous solution), or adopt the organic amine of small molecules, as first amine, ethamine, propylamine, quadrol etc. carry out de-removing, or directly adopt water to wash.In oxidation solution, so unavoidably in turn introduce basic metal or alkaline-earth metal ions and water. Basic metal or alkaline-earth metal ions (are generally Na+) de-except water-washing method can be adopted, then taken off the water removed wherein by drying treatment. By depickling, de-Na+And decompression concentrate process, it is supplied in the hydrogen phosphide cumene oxidation solution of epoxidation step, organic acid weight content is preferably��0.1%, it is more preferable to be��600ppm; Na+Weight content be preferably��500ppm, it is more preferable to be��200ppm; The weight content of water is preferably��0.2%, it is more preferable to be��0.1%.
In hydrogen phosphide cumene oxidation solution, the mensuration of organic acid content can adopt the mode of ion chromatography or acid base titration, and the mensuration of basic metal or alkaline-earth metal ions content can adopt ion chromatography, and water-content can adopt vapor-phase chromatography to measure.
In step c), as the butylene of epoxidation reaction raw material, to its purity without particular requirement, generally butylene purity is greater than 80 volume %. The form of mixtures that hydrogen phosphide cumene is generally formed with itself and isopropyl benzene as the oxygen carrier of epoxidation reaction uses, and general selects its concentration to be 1 ~ 90 weight %, it is preferable that 10 ~ 85 weight %. Concentration is too low, epoxidation inefficiency, less economical; Excessive concentration, then reaction heat effect is obvious, and reaction heat eliminates difficulty, and too high concentration causes the too high levels of benzylalcohol and other by product in product, the performance of epoxidation catalyst is unfavorable, it is easy to cause catalyst deactivation. Epoxidation reaction carries out under liquid-phase condition in solvent, and the solvent adopted is liquid under temperature of reaction and pressure, and reactant and product are inertia by it. The solvent adopted comprises benzene and the substituted benzene such as the paraffinic hydrocarbonss such as hexane, hexanaphthene, heptane, octane, nonane, decane, undecane, dodecane and benzene, toluene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene, isopropyl benzene, preferred isopropyl benzene, can avoid like this introducing extra material, increase separating energy consumption. Epoxidation reaction temperature is preferably 40 ~ 130 DEG C. Temperature is crossed low reaction and is difficult to carry out, and temperature is too high, easily causes hydrogen phosphide cumene to decompose, and by product increases. Reaction pressure is to maintain reaction raw materials in liquid, it is preferable to 0.5 ~ 8.0MPa. Hypotony easily causes material to be vaporized, and cannot ensure to carry out under liquid-phase condition, and hypertonia then causes reaction heat to increase, and power consumption is too big, affects economy. Epoxidation reaction both can carry out in slurry bed reactor, it is also possible to carries out in fixed-bed reactor. But from the angle of large-scale commercial production, it is preferred to use fixed-bed reactor. Catalyzer used is titanium-containing meso-porous or macroporous silica catalytic material Ti-HMS, Ti-MCM-41, Ti-TUD-1, Ti-SBA-15, Ti-KIT-1 or Ti-SiO2, it is possible to method preparation disclosed in document CN201010208153.7, wherein in catalyzer, titanium content is the 0.1��20% of catalyst weight, it is preferable that 0.2��10%.
In order to ensure that hydrogenolysis of alpha, alpha-dimethyl benzyl alcohol reaction can carry out smoothly, it is to increase the utilization ratio of hydrogen phosphide cumene, reduce the loss of isopropyl benzene, the transformation efficiency of hydrogen phosphide cumene will be improved as far as possible, reduce its content in epoxidation product. In general, go out butylene and butylene oxide ring through rectifying separation after, in the cumene solution of benzylalcohol being supplied to hydrogenolysis step, the weight content of hydrogen phosphide cumene should control below 3%.This can realize by improving the activity of catalyzer, it is also possible to is completed by methods such as rectifying, absorption, extractions. Pay the utmost attention to the content that methods such as adopting the activity, rectifying and the absorption that improve catalyzer reduces hydrogen phosphide cumene.
Hydrogenolysis step is �� epoxidation step produced in the presence of a catalyst, alpha-alpha-dimethyl benzylalcohol hydrogenolysis generates isopropyl benzene, this reaction carries out in solvent when gas-solid-liquid three-phase, and reactant and product are inertia and are liquid state at reaction conditions by solvent. Selected solvent comprises benzene and the substituted benzene such as the paraffinic hydrocarbonss such as hexane, hexanaphthene, heptane, octane, nonane, decane, undecane, dodecane and benzene, toluene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene, isopropyl benzene, preferred isopropyl benzene, can avoid like this introducing extra material, increase separating energy consumption. Used catalyst comprises the catalytic material that the nickel base on carriers such as being carried on activated alumina, silicon oxide, zeolite molecular sieve and gac, copper base, palladium base etc. have catalytic hydrogenolysis function. The temperature of hydrogenolysis and pressure are preferably 80 ~ 400 DEG C and 0.1 ~ 6.0MPa respectively. Hydrogenolysis both can carry out in slurry bed reactor, it is also possible to carries out in fixed-bed reactor. But from the angle of large-scale commercial production, it is preferred to use fixed-bed reactor.
The present inventor finds, the excessive concentration of Organic Acid and Base metal or alkaline-earth metal ions and water in hydrogen phosphide cumene oxidation solution, seriously can affect the selectivity of epoxidation reaction and the work-ing life of catalyzer. Only control organic acid weight percentage in hydrogen phosphide cumene oxidation solution and it is not more than 0.1%, the weight percent concentration of basic metal or alkaline-earth metal ions is not more than 500ppm, the weight percent concentration of water is not more than 0.2%, could ensure the carrying out of epoxidation reaction highly selective; Can also ensureing that catalyzer has longer work-ing life, catalyzer can improve 100% duration of service simultaneously; In addition, the inventive method is except object product butylene oxide ring, it does not have other joint product generate, and the isopropyl benzene as initial raw material can use at system internal recycle, and Technological Economy is good, achieves good technique effect.
Below by embodiment, the invention will be further elaborated.
Embodiment
[embodiment 1]
At 100 DEG C, 0.3MPa, when the mol ratio of isopropyl benzene and air is 1:5, isopropyl benzene and air carry out oxidizing reaction, obtain the hydrogen phosphide cumene oxidation solution that weight concentration is 24%.
Adopt Na2CO3Weight content is the solution washing hydrogen phosphide cumene oxidation solution of 5%, and wherein the volume ratio of oxidation solution and alkali lye is 4:1, de-except organic acid wherein. Then use deionized water wash oxidation solution, remove the Na remained because of alkali cleaning+, wherein the volume ratio of oxidation solution and deionized water is 4:1. According to epoxidation reaction needs, it being carried out vacuum concentrate, concentrate temperature 80 DEG C, obtain the oxidation solution that hydrogen phosphide cumene concentration is 50 weight %, the water remained because washing while concentrate is also removed to a certain extent. After process, the organic acid weight content in hydrogen phosphide cumene oxidation solution is the weight content of 100ppm, H2O be the weight content of 200ppm, Na+ is 50ppm.
By above-mentioned hydrogen phosphide cumene oxidation solution (CHP concentration is 50 weight %) under Ti-HMS catalyzer (Si/Ti=35) exists, in fixed-bed reactor, carry out epoxidation reaction with 1-butylene generate 1,2-butylene oxide ring and alpha, alpha-dimethyl benzyl alcohol.Wherein 1-butylene/CHP=5:1(mole), WHSV (CHP)=5 hour-1, temperature of reaction was 100 DEG C, and reaction pressure is 3MPa.
Being led to by reaction mass and reclaim excessive 1-butylene into butene recovery tower and recycle, wherein butene recovery tower operates at ambient pressure, tower top temperature-7 DEG C, bottom temperature 150 DEG C. Tower reactor enters butylene oxide ring knockout tower containing the material of 1,2-butylene oxide ring, alpha, alpha-dimethyl benzyl alcohol and isopropyl benzene etc., and this tower operates at ambient pressure, tower top temperature 65 DEG C, bottom temperature 170 DEG C.
Butylene oxide ring knockout tower tower reactor enters benzylalcohol hydrogenolysis device containing the material of alpha, alpha-dimethyl benzyl alcohol and isopropyl benzene etc. Alpha, alpha-dimethyl benzyl alcohol is at 0.5%Pd/Al2O3There is lower hydrogenolysis and generate isopropyl benzene in catalyzer. Temperature of reaction is 160 DEG C, and reaction pressure is 2.0MPa, H2The mol ratio of/alpha, alpha-dimethyl benzyl alcohol is 3:1. The isopropyl benzene generated is circulated to oxidation step as the raw material preparing hydrogen phosphide cumene. Reaction result is as shown in table 1.
[embodiment 2]
At 98 DEG C, 0.3MPa, when the mol ratio of isopropyl benzene and air is 1:5, isopropyl benzene and air carry out oxidizing reaction, obtain the hydrogen phosphide cumene oxidation solution that weight concentration is 24%.
Adopt Na2CO3Weight content is the solution washing hydrogen phosphide cumene oxidation solution of 5%, and wherein the volume ratio of oxidation solution and alkali lye is 4:1, de-except organic acid wherein. Then use deionized water wash oxidation solution, remove the Na remained because of alkali cleaning+, wherein the volume ratio of oxidation solution and deionized water is 4:1. According to epoxidation reaction needs, it being carried out vacuum concentrate, concentrate temperature 80 DEG C, obtain the oxidation solution that hydrogen phosphide cumene concentration is 50 weight %, the water remained because washing while concentrate is also removed to a certain extent. After process, the organic acid weight content in hydrogen phosphide cumene oxidation solution is 80ppm, H2The weight content of O is 150ppm, Na+Weight content be 45ppm.
By above-mentioned hydrogen phosphide cumene oxidation solution (CHP concentration is 50 weight %) under Ti-MCM-41 catalyzer (Si/Ti=40) exists, in fixed-bed reactor, carry out epoxidation reaction with 2-butylene generate 2,3-butylene oxide ring and alpha, alpha-dimethyl benzyl alcohol. Wherein 2-butylene/CHP=7:1(mole), WHSV (CHP)=5 hour-1, temperature of reaction is 98 DEG C, and reaction pressure is 3MPa.
2-butylene reclaims and product separation process same [embodiment 1], just replaces 1-butylene and 1,2-butylene oxide ring into 2-butylene and 2,3-butylene oxide ring respectively.
Butylene oxide ring knockout tower tower reactor enters benzylalcohol hydrogenolysis device containing the material of alpha, alpha-dimethyl benzyl alcohol and isopropyl benzene etc. Alpha, alpha-dimethyl benzyl alcohol hydrogenolysis under 0.2%Pd/C catalyzer exists generates isopropyl benzene. Temperature of reaction is 150 DEG C, and reaction pressure is 2.0MPa, H2The mol ratio of/alpha, alpha-dimethyl benzyl alcohol is 3:1. The isopropyl benzene generated is circulated to oxidation step as the raw material preparing hydrogen phosphide cumene. Reaction result is as shown in table 1.
[embodiment 3]
At 98 DEG C, 0.3MPa, when the mol ratio of isopropyl benzene and air is 1:5, isopropyl benzene and air carry out oxidizing reaction, obtain the hydrogen phosphide cumene oxidation solution that weight concentration is 24%.
Employing NaOH weight content is the solution washing hydrogen phosphide cumene oxidation solution of 2%, and wherein the volume ratio of oxidation solution and alkali lye is 4:1, de-except organic acid wherein. Then use deionized water wash oxidation solution, remove the Na remained because of alkali cleaning+, wherein the volume ratio of oxidation solution and deionized water is 4:1.According to epoxidation reaction needs, it being carried out vacuum concentrate, concentrate temperature 80 DEG C, obtain the oxidation solution that hydrogen phosphide cumene concentration is 60 weight %, the water remained because washing while concentrate is also removed to a certain extent. After process, the organic acid weight content in hydrogen phosphide cumene oxidation solution is 60ppm, H2The weight content of O is 100ppm, Na+Weight content be 30ppm.
By above-mentioned hydrogen phosphide cumene oxidation solution (CHP concentration is 60 weight %) under Ti-TUD-1 catalyzer (Si/Ti=40) exists, in fixed-bed reactor, carry out epoxidation reaction with iso-butylene generate 2-methyl isophthalic acid, 2-propylene oxide and alpha, alpha-dimethyl benzyl alcohol. Wherein iso-butylene/CHP=6:1(mole), WHSV (CHP)=4 hour-1, temperature of reaction is 100 DEG C, and reaction pressure is 3.5MPa.
Iso-butylene reclaims and product separation process same [embodiment 1], just replaces as iso-butylene and 2-methyl isophthalic acid respectively by 1-butylene and 1,2-butylene oxide ring, 2-propylene oxide.
2-methyl isophthalic acid, 2-propylene oxide knockout tower tower reactor enters benzylalcohol hydrogenolysis device containing the material of alpha, alpha-dimethyl benzyl alcohol and isopropyl benzene etc. Alpha, alpha-dimethyl benzyl alcohol hydrogenolysis under 0.2%Pd/C catalyzer exists generates isopropyl benzene. Temperature of reaction is 160 DEG C, and reaction pressure is 2.2MPa, H2The mol ratio of/alpha, alpha-dimethyl benzyl alcohol is 2:1. The isopropyl benzene generated is circulated to oxidation step as the raw material preparing hydrogen phosphide cumene. Reaction result is as shown in table 1.
[embodiment 4]
At 98 DEG C, 0.3MPa, when the mol ratio of isopropyl benzene and air is 1:5, isopropyl benzene and air carry out oxidizing reaction, obtain the hydrogen phosphide cumene oxidation solution that weight concentration is 24%.
Employing NaOH weight content is the solution washing hydrogen phosphide cumene oxidation solution of 2%, and wherein the volume ratio of oxidation solution and alkali lye is 4:1, de-except organic acid wherein. Then use deionized water wash oxidation solution, remove the Na remained because of alkali cleaning+, wherein the volume ratio of oxidation solution and deionized water is 4:1. According to epoxidation reaction needs, it being carried out vacuum concentrate, concentrate temperature 80 DEG C, obtain the oxidation solution that hydrogen phosphide cumene concentration is 55 weight %, the water remained because washing while concentrate is also removed to a certain extent. After process, the organic acid weight content in hydrogen phosphide cumene oxidation solution is 70ppm, H2The weight content of O is 120ppm, Na+Weight content be 40ppm.
By above-mentioned hydrogen phosphide cumene oxidation solution (CHP concentration is 60 weight %) under Ti-SBA-15 catalyzer (Si/Ti=50) exists, in fixed-bed reactor, carry out epoxidation reaction with 1-butylene generate 1,2-butylene oxide ring and alpha, alpha-dimethyl benzyl alcohol. Wherein 1-butylene/CHP=7:1(mole), WHSV (CHP)=4.5 hour-1, temperature of reaction is 100 DEG C, and reaction pressure is 3.5MPa.
1-butylene reclaims and product separation process same [embodiment 1].
1,2-butylene oxide ring knockout tower tower reactor enters benzylalcohol hydrogenolysis device containing the material of alpha, alpha-dimethyl benzyl alcohol and isopropyl benzene etc. Alpha, alpha-dimethyl benzyl alcohol is at 0.2%Pd/Al2O3There is lower hydrogenolysis and generate isopropyl benzene in catalyzer. Temperature of reaction is 160 DEG C, and reaction pressure is 2.2MPa, H2The mol ratio of/alpha, alpha-dimethyl benzyl alcohol is 2:1. The isopropyl benzene generated is circulated to oxidation step as the raw material preparing hydrogen phosphide cumene. Reaction result is as shown in table 1.
[embodiment 5]
At 100 DEG C, 0.3MPa, when the mol ratio of isopropyl benzene and air is 1:5, isopropyl benzene and air carry out oxidizing reaction, obtain the hydrogen phosphide cumene oxidation solution that weight concentration is 24%.
Adopt Na2CO3Weight content is the solution washing hydrogen phosphide cumene oxidation solution of 5%, and wherein the volume ratio of oxidation solution and alkali lye is 4:1, de-except organic acid wherein. Then use deionized water wash oxidation solution, remove the Na remained because of alkali cleaning+, wherein the volume ratio of oxidation solution and deionized water is 4:1. According to epoxidation reaction needs, it being carried out vacuum concentrate, concentrate temperature 80 DEG C, obtain the oxidation solution that hydrogen phosphide cumene concentration is 55 weight %, the water remained because washing while concentrate is also removed to a certain extent. After process, the organic acid weight content in hydrogen phosphide cumene oxidation solution is 75ppm, H2The weight content of O is 120ppm, Na+Weight content be 40ppm.
By above-mentioned hydrogen phosphide cumene oxidation solution (CHP concentration is 55 weight %) under Ti-KIT-1 catalyzer (Si/Ti=60) exists, in fixed-bed reactor, carry out epoxidation reaction with 2-butylene generate 2,3-butylene oxide ring and alpha, alpha-dimethyl benzyl alcohol. Wherein 2-butylene/CHP=6:1(mole), WHSV (CHP)=4 hour-1, temperature of reaction is 100 DEG C, and reaction pressure is 3.5MPa.
2-butylene reclaims and product separation process same [embodiment 1], just replaces 1-butylene and 1,2-butylene oxide ring into 2-butylene and 2,3-butylene oxide ring respectively.
Butylene oxide ring knockout tower tower reactor enters benzylalcohol hydrogenolysis device containing the material of alpha, alpha-dimethyl benzyl alcohol and isopropyl benzene etc. Alpha, alpha-dimethyl benzyl alcohol hydrogenolysis under 0.2%Pd/C catalyzer exists generates isopropyl benzene. Temperature of reaction is 150 DEG C, and reaction pressure is 2.0MPa, H2The mol ratio of/alpha, alpha-dimethyl benzyl alcohol is 3:1. The isopropyl benzene generated is circulated to oxidation step as the raw material preparing hydrogen phosphide cumene. Reaction result is as shown in table 1.
[embodiment 6]
At 95 DEG C, 0.25MPa, when the mol ratio of isopropyl benzene and air is 1:6, isopropyl benzene and air carry out oxidizing reaction, obtain the hydrogen phosphide cumene oxidation solution that weight concentration is 24%.
Adopt Na2CO3Weight content is the solution washing hydrogen phosphide cumene oxidation solution of 5%, and wherein the volume ratio of oxidation solution and alkali lye is 4:1, de-except organic acid wherein. Then use deionized water wash oxidation solution, remove the Na remained because of alkali cleaning+, wherein the volume ratio of oxidation solution and deionized water is 4:1. According to epoxidation reaction needs, it being carried out vacuum concentrate, concentrate temperature 80 DEG C, obtain the oxidation solution that hydrogen phosphide cumene concentration is 50 weight %, the water remained because washing while concentrate is also removed to a certain extent. After process, the organic acid weight content in hydrogen phosphide cumene oxidation solution is 120ppm, H2The weight content of O is 150ppm, Na+Weight content be 40ppm.
By above-mentioned hydrogen phosphide cumene oxidation solution (CHP concentration is 50 weight %) at Ti-SiO2Under catalyzer (Si/Ti=60) exists, in fixed-bed reactor, carry out epoxidation reaction with 1-butylene generate 1,2-butylene oxide ring and alpha, alpha-dimethyl benzyl alcohol. Wherein 1-butylene/CHP=8:1(mole), WHSV (CHP)=4.5 hour-1, temperature of reaction is 100 DEG C, and reaction pressure is 3.2MPa.
1-butylene reclaims and product separation process same [embodiment 1].
Butylene oxide ring knockout tower tower reactor enters benzylalcohol hydrogenolysis device containing the material of alpha, alpha-dimethyl benzyl alcohol and isopropyl benzene etc. Alpha, alpha-dimethyl benzyl alcohol is at 0.5%Pd/Al2O3There is lower hydrogenolysis and generate isopropyl benzene in catalyzer. Temperature of reaction is 160 DEG C, and reaction pressure is 2.0MPa, H2The mol ratio of/alpha, alpha-dimethyl benzyl alcohol is 3:1.The isopropyl benzene generated is circulated to oxidation step as the raw material preparing hydrogen phosphide cumene. Reaction result is as shown in table 1.
[comparative example 1]
With [embodiment 1], just oxidation solution is not carried out alkali cleaning, it is 800ppm, H comprising phenol at interior organic acid weight content2The weight content of O is 200ppm, Na+Weight content reach 50ppm, its reaction result is in table 2.
[comparative example 2]
With [embodiment 1], just the oxidation solution after alkali cleaning is not washed, it is 100ppm, H comprising phenol at interior organic acid weight content2The weight content of O is 180ppm, Na+Weight content reach 400ppm, its reaction result is in table 2.
[comparative example 3]
With [embodiment 1], just the oxidation solution after alkali cleaning, washing is not carried out decompression concentrate, it is 100ppm, H comprising phenol at interior organic acid weight content2The weight content 0.2%, Na of O+Weight content be 100ppm. The concentration of hydrogen phosphide cumene oxidation solution is 23.0 weight %. Its reaction result is in table 2.
[comparative example 4]
With [embodiment 1], just oxidation solution is not carried out alkali cleaning, washing, it is 700ppm, H comprising phenol at interior organic acid weight content2The weight content of O is 100ppm, Na+Weight content reach 100ppm, its reaction result is in table 2.
Table 1
Note: CHP-hydrogen phosphide cumene, BO-butylene oxide ring (represents 1,2-butylene oxide ring, 2,3-butylene oxide ring or 2-methyl isophthalic acid, 2-propylene oxide).
Table 2
Note: CHP-hydrogen phosphide cumene, BO-butylene oxide ring (represent 1,2-butylene oxide ring, 2,3-butylene oxide ring or
2-methyl isophthalic acid, 2-propylene oxide).
From the above results it can be seen that through depickling, take off Na+And the hydrogen phosphide cumene oxidation solution of decompression concentrate process, control organic acid weight percent concentration is not more than 0.3%, and the weight percent concentration of basic metal or alkaline-earth metal ions is not more than 0.1%, and the weight percent concentration of water is not more than 0.5%. Especially controlling organic acid weight percent concentration and be not more than 600ppm, the weight percent concentration of basic metal or alkaline-earth metal ions is not more than 200ppm, and the weight percent concentration of water is not more than 0.1%. High receipts rate, highly selective butylene Catalytic Oxygen can be melted into butylene oxide ring, and catalyzer has satisfactory stability.
Claims (7)
1. a production method for butylene oxide ring, comprises the following steps:
A) isopropyl benzene and air generation peroxidation, obtain hydrogen phosphide cumene oxidation solution;
B) de-except the organic acid in hydrogen phosphide cumene oxidation solution, basic metal or alkaline-earth metal ions, and water, organic acid weight percentage wherein is made to be not more than 0.1%, the weight percentage of basic metal or alkaline-earth metal ions is not more than 500ppm, and the weight percentage of water is not more than 0.2%;
C) through step b) the hydrogen phosphide cumene oxidation solution that processes and butylene are under the effect of catalyzer, and under liquid-phase condition, reaction generates butylene oxide ring and alpha, alpha-dimethyl benzyl alcohol;
D) alpha, alpha-dimethyl benzyl alcohol generates isopropyl benzene with hydrogen generation hydrogenolysis in the presence of a catalyst; The isopropyl benzene generated is circulated to step a) as the raw material preparing hydrogen phosphide cumene;
Described butylene is selected from butene-1, butylene-2 or iso-butylene, and its corresponding butylene oxide ring is respectively 1,2-butylene oxide ring, 2,3-butylene oxide ring or 2-methyl isophthalic acid, 2-propylene oxide;
Step c) reaction conditions is: temperature of reaction 25��160 DEG C, the mol ratio 1��20 of reaction pressure 0.1��10MPa, butylene and hydrogen phosphide cumene, the weight space velocity of hydrogen phosphide cumene 0.05��20 hour-1, catalyzer used is titanium-containing meso-porous or macroporous silica catalytic material Ti-HMS, Ti-MCM-41, Ti-TUD-1, Ti-SBA-15, Ti-KIT-1 or Ti-SiO2;
Described organic acid is selected from phenol.
2. the production method of butylene oxide ring according to claim 1, it is characterised in that step reaction conditions a) is: temperature of reaction 0��200 DEG C, reaction pressure 0.1��5.0MPa.
3. the production method of butylene oxide ring according to claim 1, it is characterized in that in control hydrogen phosphide cumene oxidation solution, organic acid weight percentage is not more than 600ppm, the weight percentage of basic metal or alkaline-earth metal ions is not more than 200ppm, and the weight percentage of water is not more than 0.1%.
4. the production method of butylene oxide ring according to claim 1, it is characterized in that step c) temperature of reaction is 40��130 DEG C, reaction pressure is the mol ratio of 0.5��8.0MPa, butylene and hydrogen phosphide cumene is 2��15, and the weight space velocity of hydrogen phosphide cumene is 0.1��15 hour-1��
5. the production method of butylene oxide ring according to claim 1, it is characterised in that steps d) reaction conditions be: temperature of reaction 80��400 DEG C, reaction pressure 0.1��6.0MPa.
6. the production method of butylene oxide ring according to claim 1, it is characterised in that in described hydrogen phosphide cumene oxidation solution, the concentration expressed in percentage by weight of hydrogen phosphide cumene is 1��90%.
7. the production method of butylene oxide ring according to claim 6, it is characterised in that in described hydrogen phosphide cumene oxidation solution, the concentration expressed in percentage by weight of hydrogen phosphide cumene is 10��85%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310237302.6A CN104230856B (en) | 2013-06-17 | 2013-06-17 | The production method of butylene oxide ring |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310237302.6A CN104230856B (en) | 2013-06-17 | 2013-06-17 | The production method of butylene oxide ring |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104230856A CN104230856A (en) | 2014-12-24 |
| CN104230856B true CN104230856B (en) | 2016-06-08 |
Family
ID=52219862
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310237302.6A Active CN104230856B (en) | 2013-06-17 | 2013-06-17 | The production method of butylene oxide ring |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104230856B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105315233B (en) * | 2014-07-03 | 2018-06-08 | 中国石油化工股份有限公司 | The production method of epoxy butane |
| CN104844493B (en) * | 2015-04-01 | 2017-03-15 | 中石化上海工程有限公司 | Cumyl peroxide DCP and the method for expoxy propane CHPPO coproduction |
| CN104774168B (en) * | 2015-04-01 | 2017-05-10 | 中石化上海工程有限公司 | Method for coproduction of dicumyl peroxide (DCP) and epoxybutane (CHPBO) |
| CN106279069A (en) * | 2015-08-10 | 2017-01-04 | 中国石油化工股份有限公司 | A kind of method preparing epoxy butane |
| CN107382806A (en) * | 2017-07-26 | 2017-11-24 | 江苏道明化学有限公司 | A kind of production method of cumyl peroxide |
| CN109748886B (en) * | 2017-11-01 | 2022-04-05 | 中国石油化工股份有限公司 | Method for producing epoxybutane by oxydol butylene oxide |
| CN112694380B (en) * | 2019-10-23 | 2023-03-03 | 中国石油化工股份有限公司 | Preparation method of 2, 3-dimethyl-2, 3-diphenylbutane |
| CN111807920A (en) * | 2020-07-14 | 2020-10-23 | 中国石油化工股份有限公司 | Method and system for deacidifying cumene raw material of CHPPO (chlorinated Polypropylene oxide) device |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4994586A (en) * | 1988-05-26 | 1991-02-19 | Mitsui Toatsu Chemicals, Incorporated | Method for preparing epoxy compound |
| CN1432005A (en) * | 2000-03-24 | 2003-07-23 | 住友化学工业株式会社 | Process for producing propylene oxide |
| CN1616383A (en) * | 2004-09-27 | 2005-05-18 | 华东理工大学 | Process for preparing isopropyl benzene by catalytically hydrogenolysis alpha, alpha dimethyl benzyl alcohol |
| CN1717398A (en) * | 2002-12-24 | 2006-01-04 | 昭和电工株式会社 | Method of oxidizing carbon-carbon double bond and process for producing oxidized compound |
| CN101085763A (en) * | 2007-05-11 | 2007-12-12 | 湖南长岭石化科技开发有限公司 | Method for synthesizing 1,2-epoxy butane |
| CN102295533A (en) * | 2010-06-24 | 2011-12-28 | 中国石油化工股份有限公司 | Preparation method of alpha, alpha-dimethyl benzyl alcohol |
| CN102941117A (en) * | 2012-11-13 | 2013-02-27 | 中国石油化工股份有限公司 | Regeneration method of titanium-silicon molecular sieve catalyst |
-
2013
- 2013-06-17 CN CN201310237302.6A patent/CN104230856B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4994586A (en) * | 1988-05-26 | 1991-02-19 | Mitsui Toatsu Chemicals, Incorporated | Method for preparing epoxy compound |
| CN1432005A (en) * | 2000-03-24 | 2003-07-23 | 住友化学工业株式会社 | Process for producing propylene oxide |
| CN1717398A (en) * | 2002-12-24 | 2006-01-04 | 昭和电工株式会社 | Method of oxidizing carbon-carbon double bond and process for producing oxidized compound |
| CN1616383A (en) * | 2004-09-27 | 2005-05-18 | 华东理工大学 | Process for preparing isopropyl benzene by catalytically hydrogenolysis alpha, alpha dimethyl benzyl alcohol |
| CN101085763A (en) * | 2007-05-11 | 2007-12-12 | 湖南长岭石化科技开发有限公司 | Method for synthesizing 1,2-epoxy butane |
| CN102295533A (en) * | 2010-06-24 | 2011-12-28 | 中国石油化工股份有限公司 | Preparation method of alpha, alpha-dimethyl benzyl alcohol |
| CN102941117A (en) * | 2012-11-13 | 2013-02-27 | 中国石油化工股份有限公司 | Regeneration method of titanium-silicon molecular sieve catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104230856A (en) | 2014-12-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104230856B (en) | The production method of butylene oxide ring | |
| CN104109140A (en) | Epoxypropane production method | |
| CN104277013A (en) | Method for preparing epoxybutane | |
| CN104109139A (en) | Epoxypropane synthesis method | |
| CN101279958B (en) | Method for preparing epoxy chloropropane by epoxidation of propylene chloride | |
| CN102372596B (en) | Method for producing glycol product by separating synthetic gas | |
| CN104130216A (en) | Process for continuously producing epoxy propane through propylene and propane mixed gas directly oxidized by hydrogen peroxide | |
| WO2001070710A1 (en) | Process for producing propylene oxide | |
| CN102372597B (en) | Method for separating glycol product produced from syngas | |
| CN110479037B (en) | Composite absorbent and method for separating and purifying ethylene oxide by using same | |
| CN102911137A (en) | Method for separating and recovering EO (ethylene oxide) from direct oxidation products of ethylene | |
| CN104045516B (en) | The method improving quality of ethylene glycol product | |
| CN105315237A (en) | Synthetic method of 3,4-epoxy-1-butylene | |
| CN105218485B (en) | The method for producing epoxy butane | |
| CN101367709A (en) | Method for catalysis of atmospheric oxidation cyclohexane with ultra-fine A100H-supported metalloporphyrin | |
| CN110357835B (en) | Preparation method of epichlorohydrin | |
| CN104230641B (en) | Produce the method for isopropyl benzene | |
| CN103664831A (en) | System and method for producing derivatives of olefin | |
| CN104230636B (en) | Low content hydrogenation of acetophenone is prepared the method for ethylbenzene | |
| CN104230643B (en) | Prepare the method for isopropyl benzene | |
| CN100376520C (en) | Method for producing cumene and method for producing propylene oxide including the same method | |
| CN111217771B (en) | Method for directly epoxidation of propylene and molecular oxygen | |
| CN105315236B (en) | The method for producing 3,4- epoxy-1-butylene | |
| CN114522738A (en) | Method for preparing 1, 3-propylene glycol from 3-acetoxy propionaldehyde through one-step hydrogenation | |
| CN105524027A (en) | Epoxypropane composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |