CN114349588B - Preparation method of isooctane, isododecane and isohexadecane - Google Patents
Preparation method of isooctane, isododecane and isohexadecane Download PDFInfo
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Abstract
The preparation process of isooctane, isododecane and isohexadecane with hydrogen, isobutene or residual C4 as material and assistant includes one-step synthesis of isooctane, isododecane and isohexadecane in fixed bed reactor with oligomerization-hydrogenation catalyst at certain temperature, pressure and space velocity. The method couples oligomerization and hydrogenation in the same reactor, has simple process, less investment in equipment and low energy consumption, and has remarkable economic benefit.
Description
Technical Field
The invention relates to a preparation method of isooctane, isododecane and isohexadecane.
Technical Field
Isooctane, colorless, transparent liquid, insoluble in water, inflammable, irritating and volatile; it is mainly used as additive for gasoline, aviation gasoline, etc. for regulating its octane number and nonpolar inert solvent in organic synthesis. The isomerism dodecane and the isomerism hexadecane are highly branched synthetic hydrocarbon solvent oil products, are clear, colorless and tasteless, hardly contain aromatic hydrocarbon and sulfur, are harmless to human bodies, are easy to biodegrade, have high evaporation speed and good compatibility, and are widely applied to the fields of cosmetics, metal processing, aerosol and the like.
The preparation of isooctane and isododecane by oligomerization of isobutene or mixed C4 is currently the dominant process for producing isooctane and isododecane. The CN1381548A is hydrogenated to produce isooctane after oligomerization of mixed carbon, the process uses a solid acid catalyst for contact reaction, the solid acid catalyst is a solid phosphoric acid catalyst, a hydrogen-type ZSM-5 zeolite catalyst or a small silica-alumina ball catalyst, the oligomerization is hydrogenated to produce isooctane, and the hydrogenation catalyst is a nickel-loaded hydrogenation catalyst on an alumina or zeolite carrier. US4197185 and US4244806 use C4 with an isobutene content higher than 90% as a raw material, the first step of oligomerization to form dimers and trimers, the second step of hydrogenation to form isooctane and isododecane, the catalyst used in the oligomerization is a silicon-aluminum molecular sieve catalyst, and the catalyst used in the hydrogenation is a palladium alumina or nickel alumina catalyst. US330942 uses mixed C4 as a raw material, and in the first step, solid phosphoric acid is used for catalytic oligomerization, and in the second step, a Co-Mo hydrogenation catalyst is used for catalytic hydrogenation to prepare isooctane and isododecane.
The existing process for preparing isooctane and isododecane adopts a two-step method, comprising oligomerization and hydrogenation, wherein the oligomerization adopts a solid acid catalyst, such as solid phosphoric acid, a molecular sieve and the like, and the hydrogenation adopts hydrogenation catalysts, such as palladium alumina, nickel alumina and the like. The two-step method for synthesizing isooctane and isododecane has complex process, large equipment investment and high energy consumption. Therefore, a new preparation method capable of preparing isooctane and the like in one step has been demanded.
Disclosure of Invention
The invention aims to provide a preparation method of isooctane, isododecane and isohexadecane, which adopts a one-step method to catalyze isobutene or raffinate C4 oligomerization hydrogenation to prepare isooctane, isododecane and isohexadecane products, shortens the reaction process, reduces equipment investment and energy consumption, and improves the economy of the device.
In order to achieve the above object, the present invention adopts the following technical scheme:
the preparation process of isooctane, isododecane and isohexadecane with hydrogen, isobutene or residual C4 as material and assistant includes reaction in fixed bed with oligomerization-hydrogenation catalyst. The oligomerization-hydrogenation bifunctional catalyst is a fluorine modified polystyrene sulfonic acid resin supported metal catalyst, the metal comprises one or more of I metal and one or more of II metal and one or more of III metal, wherein the I metal is one of platinum, palladium, ruthenium, rhodium, iridium, copper and zinc, preferably platinum, palladium and ruthenium, the II metal is one of nickel, iron, cobalt, scandium, titanium, vanadium, chromium, manganese, yttrium, zirconium, niobium, molybdenum, technetium, tungsten and rhenium, preferably one of nickel, iron and cobalt, and the III metal is one of lanthanide metal elements lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium, preferably lanthanum and cerium.
The preparation method of the oligomerization-hydrogenation bifunctional catalyst comprises the following steps of 1) filling polystyrene sulfonic acid resin into a reaction kettle, adding 98% concentrated sulfuric acid, sealing the reaction kettle, blowing nitrogen, introducing fluorine gas for reaction, adding water for quenching after the reaction is finished, filtering and washing to obtain fluorine modified polystyrene sulfonic acid resin; 2) Filling fluorine modified styrene sulfonic acid resin into a fixed bed, and continuously leaching the catalyst by using a mixed metal salt solution; 3) The leaching solution is taken from the outlet of the fixed bed to carry out pH value measurement, and if the pH value is between 6.5 and 7.0, leaching feeding is stopped; 4) And drying the leached catalyst, wherein the drying temperature is preferably 80-140 ℃, more preferably 100-120 ℃, and the drying time is 4-24 hours, more preferably 8-12 hours, so as to obtain the oligomerization-hydrogenation dual-function catalyst.
The preparation method of the oligomerization-hydrogenation bifunctional catalyst comprises the following steps of 1) filling polystyrene sulfonic acid resin into a polytetrafluoroethylene lining reaction kettle, adding 98% of concentrated sulfuric acid, wherein the mass of the concentrated sulfuric acid is 0.1-2 times, preferably 0.5-1 times of that of the resin, sealing the reaction kettle, purging with nitrogen, introducing fluorine gas for reaction, wherein the addition amount of the fluorine gas is 0.01-0.5, preferably 0.1-0.2, the reaction temperature is-10-10 ℃, preferably 0-5 ℃, the reaction time is 1-5h, preferably 2-4h, adding water for quenching after the reaction is finished, the water amount is 0.5-2 times, preferably 1-1.5 times of that of the fluorine gas, filtering, and washing with deionized water to obtain the fluorine modified polystyrene sulfonic acid resin. 2) Filling fluorine modified styrene sulfonic acid resin into a fixed bed, continuously leaching the catalyst by using a mixed metal salt solution, wherein the feeding airspeed of the salt solution is 0.1-5h -1 Preferably 0.5 to 1h -1 The salt solution comprises one or more of I metal salt, one or more of II metal salt and one or more of III metal salt, wherein the total mass of I metal salt, the total mass of II metal salt and the total mass ratio of III metal salt in the solution are as follows1:1:0.5-1:20:5. 3) And taking the leaching solution at the outlet of the fixed bed to measure the pH value, and stopping leaching feeding if the pH value is between 6.5 and 7.0. 4) And drying the leached catalyst to obtain the oligomerization-hydrogenation dual-function catalyst. The drying temperature is 80-140 ℃, preferably 100-120 ℃, and the drying time is 4-24 hours, preferably 8-12 hours.
The loading of the I-type metal is 1% -5% of the carrier mass, preferably 2% -4%, the loading of the II-type metal is 5% -12% of the carrier mass, preferably 9% -11%, and the loading of the III-type metal is 0.5% -3% of the carrier mass, preferably 1% -2%.
The catalyst is prepared by ion exchange of metal ions with hydrogen ions on acidic resin, the metal ions replace the hydrogen ions, and the metal ions are loaded on the resin. The II-type metal in the bifunctional catalyst has higher oligomerization activity, can generate a trimerization product of isobutene with high selectivity, has higher polymerization activity of isobutene catalyzed by lanthanide, can generate isobutene trimerization and tetramerization products with high selectivity through regulation and control of an auxiliary agent, and the I-type transition metal has higher hydrogenation activity, so that isobutene, triisobutene and tetraisobutene serving as intermediate products of isobutene oligomerization can be rapidly hydrogenated and saturated to generate isooctane, isododecane and isohexadecane products. The reaction process is as follows: after the isobutene passes through the outdiffusion and enters the catalyst pore canal, adsorption occurs, and as the oligomerization activity of the catalyst is far higher than that of hydrogenation, the isobutene firstly undergoes oligomerization reaction to generate dimers, trimers and tetramers, and the oligomerization product does not pass through the outdiffusion and is adsorbed by adjacent hydrogenation active centers to react with hydrogen, so that isooctane, isododecane and isohexadecane products are generated through hydrogenation.
Compared with the traditional polystyrene sulfonic acid resin, the polystyrene sulfonic acid resin modified by fluorine in the patent has higher oligomerization-hydrogenation activity, hydrogen on the benzene ring structure in the resin is partially replaced by fluorine atoms, fluorine has extremely small atomic radius and extremely strong electronegativity, the extremely strong electron-withdrawing effect can lead the resin to display stronger acidity, the metal subjected to exchange loading has more obvious electron-deficient characteristic, the coordination activity of II-type metal and isobutene is stronger, the oligomerization activity of the catalyst is obviously improved, the adsorption effect of I-type metal, hydrogen, isobutene dimer, trimer and tetramer is stronger, and the hydrogenation activity of the catalyst is obviously improved.
In the invention, the auxiliary agent is selected from one or more of acetonitrile, formamide, glycerol, ethylene glycol, propylene glycol, methylene dichloride and chloroform, and preferably methylene dichloride. The addition agent is used in an amount of 0.01 to 10% by mass, preferably 0.1 to 1% by mass, of the isobutene or the mixed carbon four. The addition of the auxiliary agent can regulate and control the selectivity of the oligomerization active center, the oligomerization activity of the II-type element is reduced along with the increase of the addition of the auxiliary agent, the lanthanide element has oligomerization activity only under the action of a certain auxiliary agent, the activity of the lanthanide element is firstly increased and then decreased along with the increase of the auxiliary agent, and the overall oligomerization activity is the comprehensive effect of two active sites.
In the present invention, the molar ratio of hydrogen to isobutene or raffinate C4 is from 1:1 to 10:1, preferably 1.2:1 to 3:1. the isobutene or the residual carbon number are preheated to 40-150 ℃, preferably 50-80 ℃, mixed with the auxiliary agent and hydrogen and then enter the fixed bed reactor from the upper part.
In the invention, the space velocity of the isobutene or the mixed carbon four feed is 0.1 to 10 hours -1 Preferably 0.2 to 2 hours -1 The reaction pressure is 1-10MPa, preferably 2-5MPa, and the reaction temperature is 40-250 ℃, preferably 50-200 ℃.
The oligomerization and hydrogenation-reaction heat release amount is large, isobutene or mixed carbon four are preheated to a certain temperature and then enter a reactor to react on a catalyst, the self heat release and the temperature rise are carried out, and in order to control the reaction heat, the isobutene or the residual carbon four can be diluted by a diluent before being used, preferably the diluent is selected from one or more of C4-C20 alkanes, more preferably from isooctane and/or isododecane, and/or isohexadecane; the reactor outlet feed may also be recycled back to the reactor inlet for dilution of the isobutylene or mixing of the carbon four feedstock. The reactor can adopt a pile bed or a tube array, wherein the pile bed has simple structure, low cost and convenient catalyst filling, and can be used as a preference.
Compared with the prior art, the invention has the following advantages:
the patent adopts one-step method to synthesize isooctane, isododecane and isohexadecane, oligomerization and hydrogenation are carried out in the same reactor, the equipment investment is reduced, three products can be directly produced by using the same device, the product proportion can be directly regulated and controlled, the process is simple, the intermediate does not need to be separated, the equipment investment and the energy consumption are reduced, and the cost is more advantageous.
The specific embodiment is as follows:
the present invention will be described in further detail with reference to examples, the scope of which includes but is not limited to such examples.
The analytical instrument and method for the examples are as follows:
gas chromatograph: agilent-7820;
gas chromatographic column: DB-5 capillary column with the thickness of 0.25mm multiplied by 30m, detector FID, vaporizing chamber temperature of 280 ℃, column box temperature of 280 ℃, FID detector temperature of 300 ℃, argon current-carrying capacity of 2.1mL/min, hydrogen flow of 30mL/min, air flow of 400mL/min and sample injection amount of 1.0 mu L. The conversion of the alkene and the selectivity of the product were calculated using an area normalization method. Heating program: preheating to 40 deg.C, maintaining for 5min, and heating from 40 deg.C to 280 deg.C at 15 deg.C/min for 2min.
Bromine index instrument: instrument for measuring bromine number and bromine index of Jiangsu Taizhou
ICP instrument: agilent model 7700
Example 1
(1) And (3) preparing a catalyst: filling 1500ml (1 kg) of dried A-35 resin (Dow) into a polytetrafluoroethylene lining reaction kettle, adding 2kg of 98% concentrated sulfuric acid, sealing the reaction kettle, purging with nitrogen, introducing 500g of fluorine gas for reaction at a reaction temperature of 10 ℃ for 5 hours, adding 1kg of water for quenching after the reaction is finished, filtering, washing with deionized water for multiple times, detecting that the fluorine content in the deionized water is less than 1ppm, and finishing washing to obtain the fluorine modified polystyrene sulfonic acid resin. The 1500ml fluorine modified A-35 resin is filled in a fixed bed with an inner diameter of 25mm to prepare a mixed solution of palladium nitrate, nickel nitrate and lanthanum chloride, and the concentrations are 50g/L,50g/L and 25g/L respectively. Feeding by peristaltic pump with airspeed of 0.1h -1 And taking the leaching solution from the lower outlet of the fixed bed to measure the pH value, wherein the pH value reaches 6.5-7.0, and stopping feeding. The catalyst after leaching is washed at 80 DEG CDrying for 24 hours to obtain the oligomerization-hydrogenation bifunctional catalyst, wherein the loading amount of palladium, nickel and lanthanum is 5%,5% and 0.5% by adopting ICP measurement.
(2) And (3) reaction verification: 1100ml of the bifunctional catalyst prepared in the step (1) is filled in the middle and lower parts of a fixed bed reactor with the inner diameter of 20mm, hydrogen is preheated to 100 ℃ and enters the reactor to perform catalyst activation, and the volume space velocity is 200h -1 The temperature of the reactor is 100 ℃ and the activation time is 24 hours; after the activation is finished, isobutene, glycerin and hydrogen are preheated to 40 ℃, the mixture is fed from the upper part of a fixed bed, the feeding amount of the isobutene is 110ml/h, the feeding amount of the glycerin is 0.01% of the mass of the isobutene, the feeding amount of the hydrogen is 410ml/min (standard condition), the reaction pressure is 1Mpa, no heat is removed outside the fixed bed, heat preservation is carried out by adding heat preservation cotton, sampling analysis is carried out at the outlet of the reactor, the IB conversion rate is 99%, the isooctane selectivity is 56%, the isododecane selectivity is 35%, the isohexadecane selectivity is 7%, the byproduct isobutane selectivity is 2%, and the isododecane and the isohexadecane bromine index are all less than 10.
Example 2
(1) And (3) preparing a catalyst: filling 1500ml (1 kg) of dried A-35 resin (Dow) into a polytetrafluoroethylene lining reaction kettle, adding 100g of 98% concentrated sulfuric acid, sealing the reaction kettle, purging with nitrogen, introducing 10g of fluorine gas for reaction at the reaction temperature of-10 ℃ for 1h, adding 5g of water for quenching after the reaction is finished, filtering, washing with deionized water for many times, detecting that the fluorine content in the deionized water is less than 1ppm, and finishing washing to obtain the fluorine modified polystyrene sulfonic acid resin. The 1500ml fluorine modified A-35 resin is filled in a fixed bed with an inner diameter of 25mm to prepare a mixed solution of palladium nitrate, nickel sulfate and cerium chloride, wherein the concentrations are 5g/L,100g/L and 25g/L respectively. Feeding by peristaltic pump with airspeed of 5h -1 And taking the leaching solution from the lower outlet of the fixed bed to measure the pH value, wherein the pH value reaches 6.5-7.0, and stopping feeding. And drying the leached catalyst at 140 ℃ for 4 hours to obtain the oligomerization-hydrogenation bifunctional catalyst, wherein the loading amounts of palladium, nickel and cerium are 1%,12% and 3% by adopting ICP measurement.
(2) And (3) reaction verification: 1100ml of the bifunctional catalyst prepared in the step (1) was charged in the middle and lower part of a fixed bed reactor having an inner diameter of 20mm, and hydrogen was pre-chargedThe mixture is heated to 200 ℃ and enters a reactor to activate the catalyst, and the volume space velocity is 200h -1 The reaction temperature is 200 ℃, and the activation time is 48 hours; after the activation is finished, isobutene, propylene glycol and hydrogen are preheated to 150 ℃, the mixture is fed from the upper part of a fixed bed, the isobutene feed amount is 11L/h, the propylene glycol feed amount is 10% of the isobutene mass, the hydrogen feed amount is 40L/min (standard condition), the reaction pressure is 10Mpa, the outside of the fixed bed is subjected to heat transfer by using an oil bath at 80 ℃, the IB conversion rate is 98.1% by sampling analysis at the outlet of the reactor, the isooctane selectivity is 92%, the isododecane selectivity is 5%, the isohexadecane selectivity is 2%, the byproduct isobutane selectivity is 1%, and the isododecane and the isohexadecane bromine index are all less than 10.
Example 3
(1) And (3) preparing a catalyst: filling 1500ml (1 kg) of dried A-35 resin (Dow) into a polytetrafluoroethylene lining reaction kettle, adding 500g of 98% concentrated sulfuric acid, sealing the reaction kettle, purging with nitrogen, introducing 100g of fluorine gas for reaction at a reaction temperature of 0 ℃ for 2 hours, adding 100g of water for quenching after the reaction is finished, filtering, washing with deionized water for multiple times, detecting that the fluorine content in the deionized water is less than 1ppm, and finishing washing to obtain the fluorine modified polystyrene sulfonic acid resin. The 1500ml fluorine modified A-35 resin is filled in a fixed bed with an inner diameter of 25mm to prepare a mixed solution of palladium chloride, nickel sulfate and ytterbium nitrate, wherein the concentrations are respectively 10g/L,45g/L and 5g/L. Feeding by peristaltic pump with airspeed of 0.5h -1 And taking the leaching solution from the lower outlet of the fixed bed to measure the pH value, wherein the pH value reaches 6.5-7.0, and stopping feeding. And drying the leached catalyst at 100 ℃ for 8 hours to obtain the oligomerization-hydrogenation bifunctional catalyst, wherein the loading amounts of palladium, nickel and ytterbium are 2%,9% and 1% by adopting ICP (inductively coupled plasma) measurement.
(2) And (3) reaction verification: 100ml of the bifunctional catalyst prepared in the step (1) is filled at the middle and lower parts of a fixed bed reactor with the inner diameter of 20mm, hydrogen is preheated to 100 ℃ and enters the reactor to perform catalyst activation, and the volume space velocity is 200h -1 The temperature of the reactor is 100 ℃ and the activation time is 24 hours; after the activation, isobutene was diluted to a mass concentration of 30% by using isooctane, mixed with acetonitrile and hydrogen, preheated to 50℃and fed from the upper part of the fixed bed, the isobutene feed amount was 20ml/h,the acetonitrile feed amount is 0.01% of the isobutene mass, the hydrogen feed amount is 88ml/min (standard condition), the reaction pressure is 2Mpa, no heat transfer exists outside the fixed bed, heat preservation is carried out by adding heat preservation cotton, the IB conversion rate is 99.8% by sampling analysis at the outlet of the reactor, the isooctane selectivity is 21%, the isododecane selectivity is 65%, the isohexadecane selectivity is 12%, the byproduct isobutane selectivity is 2%, and the isododecane and the isohexadecane bromine index are all less than 10.
Example 4
(1) And (3) preparing a catalyst: filling 1500ml (1 kg) of dried A-35 resin (Dow) into a polytetrafluoroethylene lining reaction kettle, adding 1000g of 98% concentrated sulfuric acid, sealing the reaction kettle, purging with nitrogen, introducing 200g of fluorine gas for reaction at a reaction temperature of 5 ℃ for 4 hours, adding 300g of water for quenching after the reaction is finished, filtering, washing with deionized water for multiple times, detecting that the fluorine content in the deionized water is less than 1ppm, and finishing washing to obtain the fluorine modified polystyrene sulfonic acid resin. The 1500ml fluorine modified A-35 resin is filled in a fixed bed with an inner diameter of 25mm to prepare copper sulfate, zinc sulfate, cobalt sulfate, ferric sulfate, nickel sulfate, lanthanum sulfate and cerium nitrate, wherein the concentrations of copper, zinc, cobalt, iron, nickel, lanthanum and cerium ions are 20g/L,20g/L,30g/L,40g/L,40g/L,10g/L and 10g/L respectively. Feeding by peristaltic pump with airspeed of 0.5h -1 And taking the leaching solution from the lower outlet of the fixed bed to measure the pH value, wherein the pH value reaches 6.5-7.0, and stopping feeding. And drying the leached catalyst at 120 ℃ for 12 hours to obtain the oligomerization-hydrogenation dual-function catalyst, wherein the loading amount of copper, zinc, cobalt, iron, nickel, lanthanum and cerium is 2%,2%,3%,4%,4%,1% and 1% by adopting ICP (inductively coupled plasma) measurement.
(2) And (3) reaction verification: 600ml of the bifunctional catalyst prepared in the step (1) is filled at the middle and lower parts of a fixed bed reactor with the inner diameter of 20mm, hydrogen is preheated to 200 ℃ and enters the reactor for catalyst activation, and the volume space velocity is 200h -1 The reaction temperature is 200 ℃, and the activation time is 48 hours; after the activation, the isobutene, the methylene dichloride and the hydrogen are mixed and then preheated to 80 ℃, the mixture is fed from the upper part of a fixed bed, the feeding amount of the isobutene is 1200ml/h, the feeding amount of the methylene dichloride is 1% of the mass of the isobutene, the feeding amount of the hydrogen is 13.2L/min (standard condition), the reaction pressure is 5Mpa,the fixed bed adopts oil bath heat removal, the temperature of the oil bath is 80 ℃, the IB conversion rate of the reactor outlet sampling analysis is 99.7%, the isooctane selectivity is 18%, the isododecane selectivity is 68%, the isohexadecane selectivity is 13%, the byproduct isobutane selectivity is 1%, and the isododecane and the isohexadecane bromine index are all less than 10.
(3) The hydrogenated reaction liquid is recycled to the inlet of the reactor to be mixed with isobutene, the concentration of isobutene is diluted to 50wt% by the hydrogenated reaction liquid, the rest conditions are unchanged, the IB conversion rate is 99.7% by sampling analysis at the outlet of the reactor, the isooctane selectivity is 21%, the isododecane selectivity is 65%, the isohexadecane selectivity is 14%, and the isododecane and the isohexadecane bromine indexes are less than 10.
Example 5
(1) And (3) preparing a catalyst: 1500ml (1 kg) of dried A-35 resin (Dow) is filled in a polytetrafluoroethylene lining reaction kettle, 800g of 98% concentrated sulfuric acid is added, the reaction kettle is closed, after nitrogen purging is adopted, 150g of fluorine gas is introduced for reaction, the reaction temperature is 2 ℃, the reaction time is 3 hours, 180g of water quenching is added after the reaction is finished, filtering is carried out, deionized water is used for washing for many times, the fluorine content in the deionized water is detected to be less than 1ppm, and the washing is finished, so that the fluorine modified polystyrene sulfonic acid resin is obtained. The 1500ml fluorine modified A-35 resin is filled in a fixed bed with an inner diameter of 25mm to prepare platinum nitrate, palladium nitrate, nickel sulfate and ytterbium nitrate, and the concentrations are 15g/L,15g/L,80g/L and 15g/L respectively. Feeding by peristaltic pump with airspeed of 0.5h -1 And taking the leaching solution from the lower outlet of the fixed bed to measure the pH value, wherein the pH value reaches 6.5-7.0, and stopping feeding. And drying the leached catalyst at 120 ℃ for 12 hours to obtain the oligomerization-hydrogenation bifunctional catalyst, wherein the loading amounts of platinum, palladium, nickel and ytterbium are 1.5%,1.5%,8% and 1.5% by adopting ICP measurement.
(2) And (3) reaction verification: 1000ml of the bifunctional catalyst prepared in the step (1) is filled at the middle and lower parts of a fixed bed reactor with the inner diameter of 20mm, hydrogen is preheated to 100 ℃ and enters the reactor for catalyst activation, and the volume space velocity is 200h -1 The temperature of the reactor is 100 ℃ and the activation time is 24 hours; after the activation is finished, the residual carbon tetra (isobutene content 28 wt%), formamide and hydrogen are preheated to 70 ℃ from solidFeeding at the upper part of the fixed bed, wherein the feeding amount of isobutene is 1000ml/h, the feeding amount of formamide is 0.5% of the mass of isobutene, the feeding amount of hydrogen is 10L/min (standard condition), the reaction pressure is 4Mpa, the external heat preservation of the fixed bed is carried out, the sample analysis IB conversion rate at the outlet of the reactor is 99.8%, the isooctane selectivity is 20%, the isododecane selectivity is 71%, the isohexadecane selectivity is 7%, the selectivity of by-product isobutane is 2%, and the isododecane and the bromine index of the isohexadecane are all less than 10.
Comparative example:
using the A-35 resin (Dow), the other catalyst preparation and reaction procedures were the same as in example 1 except that the fluorine modification step was omitted, the IB conversion was 91%, the isooctane selectivity was 66%, the isododecane selectivity was 28%, the isohexadecane selectivity was 4%, the by-product isobutane selectivity was 2%, and the isododecane and the isohexadecane bromine indices were 35.
Claims (18)
1. A preparation method of isooctane, isododecane and isohexadecane is characterized by comprising the following steps: the method takes hydrogen, isobutene or raffinate C4 as raw materials, auxiliaries are added, isooctane, isododecane and isohexadecane are prepared by reaction in a fixed bed filled with an oligomerization-hydrogenation dual-function catalyst, the oligomerization-hydrogenation dual-function catalyst is a fluorine modified polystyrene sulfonic acid resin supported metal catalyst, the metal comprises one or more of I metals and one or more of II metals and one or more of III metals, wherein the I metals are platinum, palladium, ruthenium, rhodium, iridium, copper and zinc, the II metals are nickel, iron, cobalt, scandium, titanium, vanadium, chromium, manganese, yttrium, zirconium, niobium, molybdenum, technetium, tungsten and rhenium, the III metals are lanthanide metals lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium and lutetium, and the fluorine modified polystyrene sulfonic acid resin is prepared by the following steps: filling polystyrene sulfonic acid resin into a reaction kettle, adding 98% concentrated sulfuric acid, sealing the reaction kettle, blowing nitrogen, introducing fluorine gas for reaction, adding water for quenching after the reaction is finished, filtering, and washing to obtain fluorine modified polystyrene sulfonic acid resin.
2. The method according to claim 1, characterized in that: the loading amount of the I-type metal is 1-5% of the mass of the carrier, the loading amount of the II-type metal is 5-12% of the mass of the carrier, and the loading amount of the III-type metal is 0.5-3% of the mass of the carrier.
3. The method of claim 2, wherein the loading of the class I metal is 2-4% of the mass of the support, the loading of the class II metal is 9-11% of the mass of the support, and the loading of the class III metal is 1% -2% of the mass of the support.
4. The method according to claim 1, characterized in that: the preparation method of the oligomerization-hydrogenation bifunctional catalyst comprises the following steps of 1) filling polystyrene sulfonic acid resin into a reaction kettle, adding 98% concentrated sulfuric acid, sealing the reaction kettle, blowing nitrogen, introducing fluorine gas for reaction, adding water for quenching after the reaction is finished, filtering and washing to obtain fluorine modified polystyrene sulfonic acid resin; 2) Filling fluorine modified styrene sulfonic acid resin into a fixed bed, and continuously leaching the catalyst by using a mixed metal salt solution; 3) The leaching solution is taken from the outlet of the fixed bed to carry out pH value measurement, and if the pH value is between 6.5 and 7.0, leaching feeding is stopped; 4) And drying the leached catalyst to obtain the oligomerization-hydrogenation dual-function catalyst.
5. The method according to claim 4, wherein: the drying temperature in the step 4) is 80-140 ℃ and the drying time is 4-24h.
6. The method according to claim 4, wherein: in step 1), the mass of the concentrated sulfuric acid is 0.1 to 2 times of the mass of the polystyrene sulfonic acid resin, and/or the adding amount of the fluorine gas is 0.01 to 0.5 times of the mass of the polystyrene sulfonic acid resin, and/or the reaction temperature is-10 to 10 ℃, the reaction time is 1 to 5 hours, and/or the quenching water amount is 0.5 to 2 times of the mass of the fluorine gas.
7. The method according to claim 6, wherein: in the step 1), the mass of the concentrated sulfuric acid is 0.5-1 times of the mass of the polystyrene sulfonic acid resin, and/or the adding amount of the fluorine gas is 0.1-0.2 times of the mass of the polystyrene sulfonic acid resin, and/or the reaction temperature is 0-5 ℃, the reaction time is 2-4 hours, and/or the quenching water amount is 1-1.5 times of the mass of the fluorine gas.
8. The method according to claim 4 or 5, characterized in that: in step 2), the feeding space velocity of the metal salt solution is 0.1 to 5h -1 The total mass ratio of the I-class metal salt to the II-class metal salt to the III-class metal salt in the metal salt solution is 1:1:0.5-1:20:5.
9. The method according to claim 8, wherein: in step 2), the feeding space velocity of the metal salt solution is 0.5 to 1h -1 。
10. The method according to any one of claims 1-7, wherein: the auxiliary agent is selected from one or more of acetonitrile, formamide, glycerol, ethylene glycol, propylene glycol, methylene dichloride and chloroform; and/or the dosage of the auxiliary agent is 0.01-10% of the mass of isobutene or residual carbon four.
11. The method according to any one of claims 1-7, wherein: the molar ratio of hydrogen to isobutene or residual carbon number four is 1:1 to 10:1.
12. The method according to any one of claims 1-7, wherein: the molar ratio of hydrogen to isobutene or raffinate C4 is 1.2:1 to 3:1.
13. the method according to any one of claims 1-7, wherein: preheating isobutene or residual carbon IV to 40-150 ℃, mixing with an auxiliary agent and hydrogen, and then entering a fixed bed reactor from the upper part; and/or, the space velocity of the isobutene or the residual carbon four feed is 0.1 to 10h -1 The reaction pressure is 1-10MPa, and the reaction temperature is 40-250 ℃.
14. The method according to claim 13, wherein: preheating isobutene or residual carbon IV to 50-80 ℃, mixing with an auxiliary agent and hydrogen, and then entering a fixed bed reactor from the upper part; and/or, the space velocity of the isobutene or the residual carbon four feed is 0.2 to 2h -1 The reaction pressure is 2-5Mpa, and the reaction temperature is 50-200 ℃.
15. The method according to any one of claims 1-7, wherein: the fixed bed is an adiabatic pile bed or a tubular fixed bed.
16. The method according to any one of claims 1-7, wherein: the isobutene or the residual carbon four can be diluted by a diluent before use; the diluent is selected from one or more of C4-C20 alkane.
17. The method according to claim 16, wherein: the diluent is selected from isooctane and/or isomerised dodecane, and/or isomerised hexadecane, isobutene or raffinate carbon four concentration diluted to 10% to 100%.
18. The process of any one of claims 1-7, further comprising recycling the reactor outlet material back to the reactor inlet for dilution of isobutylene or raffinate carbon four feedstock.
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