CN1834074A - Solid acid alkylating process of isomerized alkane and olefin - Google Patents
Solid acid alkylating process of isomerized alkane and olefin Download PDFInfo
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- CN1834074A CN1834074A CN 200510053489 CN200510053489A CN1834074A CN 1834074 A CN1834074 A CN 1834074A CN 200510053489 CN200510053489 CN 200510053489 CN 200510053489 A CN200510053489 A CN 200510053489A CN 1834074 A CN1834074 A CN 1834074A
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Abstract
This invention discloses a method to alkylize isomerous alkanes and alkenes by solid acid. It is unique that in raw materials for alkylization reactions, isomerous alkanes and alkenes have a total molar ratio of 1~15. Alkenes are divided into n shares, with which isomerous alkanes are mixed in turn and go through solid acid in alkylization conditions, and then alkylized products are recycled. Here, n is not less than 2 and not more than 34. This method significantly promotes the yield of terminal product trimethylpentane, raises the octane number of alkylized petrol and enhances the stability of solid acid.
Description
Technical field
The present invention relates to a kind of alkylation, further say so about the solid acid alkylating process of a kind of isoparaffin and alkene.
Background technology
Many hydrocarbon conversion reaction technologies that adopt solid acid catalyst are at low temperatures arranged, as alkylation (alkylation of the alkylation of isoparaffin and alkene, benzene and alkene), isomerization (C
4-C
7The isomerization of low-carbon (LC) normal paraffin, the isomerization of low-carbon alkene), olefin oligomerization, hydroisomerization etc.The solid acid catalyst that in these low temperature hydrocarbon conversion reaction technologies, needs to have strong acid character, as: carried heteropoly acid catalyst, carried heteropoly acid salt catalyst, zeolite [molecular sieve, SO
4 2/ oxide compound super acidic catalyst, loading type Br nsted-Lewis conjugation solid super acid catalyst, solid polymerization ion exchange resin and Br nsted acid or acid-treated oxide compound of Lewis or molecular sieve catalyst.
In general, the alkylation of said isoparaffin and alkene is meant C
4-C
6Isoparaffin and C
3-C
6The singly-bound olefine reaction generate the process of the long chain alkane of isomery.The product of this alkylated reaction, as: the C that Trimethylmethane and butene alkylation generate
8The octane-iso hydrocarbon has high octane value and low Reid vapour pressure, is a kind of gasoline blend component of excellent performance.
Adopt H in the petroleum refining industry
2SO
4Produce alkylate oil existing decades of history with the HF method, at present, the catalyzer of employing is that concentration is about 95% H
2SO
4Or HF liquid acid.Wherein, H
2SO
4Alkylation carries out under low temperature (about 10 ℃ of temperature of reaction), can prevent the building-up reactions of alkene, generates heavy reaction product, H
2SO
4To produce a large amount of spent acid in the method alkylation process, more difficult giving birth to used, if discharging will cause serious environmental to pollute; The temperature of reaction of HF alkylation is generally 20～40 ℃, and HF acid highly volatile causes the harm of environmental pollution and production environment easily, has great potential safety hazard.About H
2SO
4Discussion visible " the Alkylation of isobutane with C detailed with the HF method
4Olefins ", " Ind.Eng.Chem.Res., 27,381-379 (1988) ", " Handbook of PetroleumRefining Processes, 1,23-28 (1986) " and " Chinese oil Refining Technologies, p206-217 (Sinopec press, 1991) ".
Because H
2SO
4With HF liquid strong acid serious environment pollution and great potential safety hazard, adopt solid acid to replace they have become investigators in the international catalytic field as the catalyzer of alkylated reaction important subject.In recent years, be used for the existing many reports of the various solid acid catalysts of abovementioned alkyl method and reaction method, for example, JP01,245,853, US3,962,133, US4,116,880, GB1,432,720, GB1,389,237 disclosed SO
4 2-/ oxide compound super acidic catalyst; US5,220,095, US5,731,256, US5,489,729, US5,364,976, US5,288,685, EP0,714,871 disclosed CF
3SO
3The H/ silicon oxide catalyst; US5,391,527, US5,739,074 disclosed Pt-AlCl
3-KCl/Al
2O
3Catalyzer; US5,157,196, US5,190,904, US5,346,676, US5,221,777, US5,120,897, US5,245,101, US5,012,033, US5,157,197, CN1,062,307, WO95/26,815, disclosed Lewis acid such as SbF
5, BF
3, AlCl
3The catalyzer of load; CN1,184,797, CN981,016,170, US5,324,881, US5,475,178 disclosed carried heteropoly acid catalysts; US3,549,557,3,644,565,3,647,916, US3,917,738, US4,384,161 disclosed molecular sieve catalysts.
WO94/03415 discloses the alkylation of a kind of alkane and alkene, this method is included under the alkylation reaction condition, in the presence of a kind of crystalline microporous body, a kind of olefin feedstock that contains is contacted with a kind of raw material that contains isoparaffin, alkylation reaction condition comprises temperature in the critical temperature of described raw material main ingredient or more than the critical temperature, and pressure is in the emergent pressure of described raw material main ingredient or more than the emergent pressure.Described crystalline microporous body comprises various zeolites and stratified material, and described zeolite comprises ZSM series zeolite, offretite zeolite, MCM zeolite, mordenite, REY zeolite etc., and layered material comprises layered silicate, laminated clay etc.When being catalyzer with the MCM series zeolite, can improve the transformation efficiency of butylene and improve activity of such catalysts stability, but this method olefin conversion is still lower, butene conversion has only the heavy % of 86.0-99.4.
CN1,125,639A discloses the alkylation of a kind of Trimethylmethane and alkene, and this method comprises PW
12, PMo
12, SiW
12, PW
12Mo
12-n(n=1-11) etc. heteropolyacid is dissolved in the mixed solution equal solvent of low carbon fatty acid, ester, ketone, ether, alcohol or lipid acid and Fatty Alcohol(C12-C14 and C12-C18) by 10～70% and makes catalyzer, the alkylated reaction of catalyzing iso-butane alkane and butylene, be reflected at 10～70 ℃ and carry out, alkane alkene ratio is 1.5～18.Though when adopting this method to avoid sulfuric acid or hydrofluoric acid to make catalyzer to the deep-etching of equipment, carry out but be reflected in the liquid phase, brought the problem of reaction product and described separated from solvent, olefin conversion and alkylate oil yield are lower when carrying out the alkylated reaction of Trimethylmethane and butylene with this method simultaneously, as record according to the example 1～9, carry out alkylated reaction in batch reactor, the alkylate oil yield has only 0.693～1.736 (in alkene weight).
CN 1,125,640A discloses the alkylation of a kind of Trimethylmethane and butylene, it is catalyzer that this method adopts the basic metal or the ammonium salt of phosphorus tungsten, phosphorus molybdenum, silicon tungsten, silicon-molybdenum heteropoly acid, the mobility scale of basic metal and ammonium ion (mol) is a phosphorus series 0.5～3.0, silicon series 0.5～4.0, the temperature of alkylated reaction are 30 ℃, and alkane alkene ratio is 15: 1.When adopting this method to carry out the alkylated reaction of Trimethylmethane and butylene, its alkylate oil yield is still lower, and can not keep activity of such catalysts stability,, in batch reactor, carry out the alkylated reaction of Trimethylmethane and butylene for example according to the record of the example, in alkene weight, the yield of alkylate oil is the highest can only to reach 1.854, and with the increase of reaction times, catalyst activity descends rapidly, as record, with Cs according to the example 1
2.5H
0.5PW
12Be catalyzer, in reactor, add alkene 0.4378 gram and alkane alkene than the alkane that is 15, in 30 ℃ of reactions 2 hours, get alkylate oil 0.8118 gram, the alkylate oil yield is 1.854, isolate catalyzer, use down in similarity condition once more after 2 hours in 100 ℃ of oven dry, the alkylate oil yield reduces to 1.384.
US 5,24, and 881 disclose the alkylation of a kind of isoparaffin and alkene, and this method is included under the alkylation conditions, in the presence of a kind of carried heteropoly acid catalyst, isoparaffin and alkene reacted, and obtain alkylate.Described heteropolyacid contains and at least aly is selected from down element in the group as its central element: P, Si, B, Ge, As, Ti, Zr, Mn, F, V, Ce, Th, and contains and at least aly be selected from down element in organizing as its coordination element: Mo, W, V, Mn, Co, Ni, Cu, Zn, Fe.This method catalyst system therefor is a kind of heteropolyacid catalyst of loading type, and according to example record, all heteropolyacid catalysts are all being handled more than 350 ℃, and its olefin conversion is the highest to have only 87 to weigh %, C
5 +The alkylate oil yield is the highest to have only 1.4 gram/gram C
4 =, experimental results show that this method of employing, catalyst activity stability is still bad.
US 5,391,527 and US 5,739,074 alkylation of a kind of isoparaffin and alkene is disclosed.This method is at Pt-KCl-AlCl
3/ Al
2O
3Under the existence of catalyzer, temperature of reaction is 30 ℃, and reaction pressure is 31 normal atmosphere, and weight space velocity is 0.2 hour
-1Alkylation reaction condition under, in a liquid phase moving-burden bed reactor, carry out alkylated reaction.This method is behind catalyst deactivation, and with Trimethylmethane and hydrogen regeneration, processing method is very complicated.
US 5,220,095 and US 5,245,100 alkylation of a kind of isoparaffin and alkene is disclosed.This method is included under the alkylation reaction condition, at the catalyzer CF of liquid acid load
3SO
3H/SiO
2Existence under, in fixed-bed reactor, carry out alkylated reaction.The liquid acid of this method load can't load on the carrier securely, runs off easily.
CN 1,232,814A discloses the alkylation reaction method of a kind of low-carbon (LC) isoparaffin and alkene, this method working load type heteropolyacid catalyst, and be not less than the critical temperature of isoparaffin in temperature, pressure is not less than under the condition of emergent pressure of isoparaffin and reacts, and has olefin conversion and the high advantage of alkylate oil yield, and activity of such catalysts stability makes moderate progress simultaneously.
CN 1,246,467A discloses the alkylation reaction method of a kind of low-carbon (LC) isoparaffin and alkene, it is characterized in that employed catalyzer is made up of a kind of Lewis acid institute of a kind of Br nsted acid of a kind of porous inorganic carrier of 40～95 heavy % and load 1～60 heavy % on it and 0.3～15 heavy %, wherein said Br nsted acid is a kind of heteropolyacid or inorganic mineral acid, and said Lewis acid is selected from AlCl
3, BF
3Perhaps XF
5, wherein X is P, As, Sb or Bi.The catalyst activity component be difficult for to run off when adopting this method, and reaction conversion ratio and selectivity are all higher.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of better isoparaffin of selectivity of alkylated reaction and the solid acid alkylating process of alkene.
The alkylated reaction of Trimethylmethane and butylene at first produces the tertiary butyl carbonium ion (i-C of butylene absorption in the heart in catalyst acid
4 +), it and C
4Generate i-C behind the olefine reaction
8 +Carbonium ion, i-C
8 +Carbonium ion can obtain purpose reaction product octane-iso and i-C from desorption on the acid sites of catalyzer after carrying out hydrogen transfer reactions with the Trimethylmethane molecule
4 +Carbonium ion, i-C
4 +Carbonium ion continues to participate in the catalytic cycle of alkylated reaction.In addition, i-C
8 +Carbonium ion can with C
4Olefine reaction generates C
12 +Carbonium ion.C
12 +Carbonium ion can generate heavy reaction product by hydrogen transfer reactions desorption in the heart from acidity of catalyst, also can cracking generates the carbonium ion and the alkene of low-carbon (LC).In most of the cases, olefin hydrocarbon molecules promptly is adsorbed on the acid site, form carbonium ion or with other carbonium ions reactions.After hydrogen transfer reactions, formed undesirable by product C
5～C
7And C
9 +
Contriver's discovery, when the alkylated reaction material of high Trimethylmethane/butylene mol ratio contacts with the solid acid catalyst acid sites, the i-C that adsorbs in the heart in the acidity of catalyst
8 +To there be a large amount of Trimethylmethane molecules around the carbonium ion, therefore, i-C
8 +Carrying out the speed of hydrogen transfer reactions between carbonium ion and the Trimethylmethane molecule will accelerate, and this is favourable to generating purpose product trimethylpentane (TMP); Simultaneously, high hydrogen transfer reactions speed can reduce the possibility of purpose product TMP to favourable low octane rating component dimethylhexane (DMH) isomery of thermodynamics, also can reduce i-C
8 +Carbonium ion and C
4Alkene continues reaction and generates heavy reaction product.
Therefore, based on above-mentioned discovery, the solid acid alkylating process of isoparaffin provided by the invention and alkene, it is characterized in that total mol ratio of isoparaffin and alkene is 1～15 in the alkylated reaction raw material of this method, alkene is divided into n part, with the isoparaffin order and the 1st to n part alkene under alkylation reaction condition by solid acid catalyst, reclaim alkylate then, wherein, 2≤n≤34.
In the method provided by the invention, said isoparaffin is C
4To C
6, wherein be preferably Trimethylmethane; Said alkene is C
3To C
6Singly-bound alkene, said singly-bound alkene is iso-butylene, butene-1, butene-2 or its mixture.
In the method provided by the invention, said alkylation reaction condition is that 10～350 ℃, the weight space velocity (WHSV) of 0.5～10.0MPa, reaction raw materials are 0.1～20 hour
-1Preferred temperature is from the critical temperature to 300 of said isoparaffin ℃, more preferably from the critical temperature to 250 of said isoparaffin ℃, preferably from the critical temperature to 200 of said isoparaffin ℃; Preferred pressure be emergent pressure from said isoparaffin to 10.0MPa, more preferably from the emergent pressure of said isoparaffin to 9.0MPa, preferably from the emergent pressure of said isoparaffin to 6.0MPa; The scope of the weight space velocity of reaction raw materials is 0.1～20 hour
-1, preferred 0.5～8.0 hour
-1
In the method provided by the invention, can adopt the mode of in alkylation reactor, said each part alkene being injected along the axial different positions place of solid acid catalyst bed to realize that wherein isoparaffin is 15～500, preferred 60～300 with the mol ratio that each part alkene contacts at beds; Also can adopt at alkylation reaction zone and set up n placed in-line alkylation reactor, the mode that said each part alkene was injected before each reactor realizes that wherein isoparaffin is 15～500, preferred 60～300 with the mol ratio that each part alkene contacts in each alkylation reactor.The preferred fixed-bed reactor of above-mentioned said alkylation reactor, the flow pattern of material can be upstriker or downstriker.
In method provided by the invention, said n is preferably 4≤n≤20, and said alkene preferably is split into n part of five equilibrium.
In the method provided by the invention, said solid acid catalyst can be the disclosed various solid acid catalysts that are used for isoparaffin and olefin alkylation reaction in the prior art, and the present invention there is no special requirement to this.Said solid acid catalyst comprises carried heteropoly acid catalyst, load or not carried heteropoly acid salt catalyst, zeolite [molecular sieve, SO
4 2-/ oxide compound super acidic catalyst, loading type Br nsted-Lewis conjugation solid super acid catalyst or Br nsted acid or acid-treated oxide compound of Lewis or molecular sieve catalyst.In above-mentioned listed catalyzer, preferably carried heteropoly acid catalyst, load or not carried heteropoly acid salt catalyst, loading type Br nsted-Lewis conjugation solid super acid catalyst or Br nsted acid or the acid-treated oxide compound of Lewis, more preferably carried heteropoly acid catalyst and loading type Br nsted-Lewis conjugation solid super acid catalyst.
Carried heteropoly acid catalyst is that porous inorganic carrier and a kind of heteropolyacid are formed.Said heteropolyacid general formula is H
8-n[AM
12O
40], wherein A is P or Si, and M is W or Mo, and n is the valence state of A, and its value is 4 or 5; Said porous inorganic carrier is conventional porous inorganic carrier, comprise aluminosilicate zeolite, carbon fiber, natural clay of gac, silicon oxide, aluminum oxide, magnesium oxide, titanium oxide, natural or synthetic etc., or their mixture, wherein preferably silicon oxide, aluminum oxide or their mixture are described this catalyzer is existing in CN1232814A.In addition, said load or carried heteropoly acid salt catalyst and above-mentioned catalyzer are not similar, different is an alkali metal salt and the ammonium salt that wherein said heteropolyacid salt is above-mentioned heteropolyacid.
Other catalyzer described in the method provided by the invention all are corresponding catalyst of the alkylated reaction that is used for isoparaffin and alkene of disclosed routine in the prior art, and the present invention also has no particular limits it.
The alkylation reaction technique method of the isoparaffin of solid acid catalysis provided by the invention and alkene, the selectivity that the makes alkylated reaction especially yield of purpose product trimethylpentane can significantly improve, the octane value of gasoline alkylate improves, and makes the stability of solid acid catalyst better simultaneously.
Description of drawings
Fig. 1 is the basic procedure synoptic diagram of the many beds fixed bed that provides of the present invention.Under alkylation reaction condition, (with the isobutane feedstock is example to isoparaffin, isobutane feedstock is made of fresh isobutane and recycle isobutane) enter from the inlet of fixed-bed reactor, olefin feed is divided into the inlet that n part enters the beds of different axial positions in the reactor respectively, enter first beds after isobutane feedstock and the first part of olefin and begin alkylated reaction, exit at first beds, alkene is by complete reaction, enter second beds after remaining Trimethylmethane and second part of olefin, and the like, flow out n beds until remaining Trimethylmethane and reaction product and enter fractionating system.
Fig. 2 is the basic procedure synoptic diagram of the n that provides of the present invention series connection fixed bed.Under alkylation reaction condition, (with the isobutane feedstock is example to isoparaffin, isobutane feedstock is made of fresh isobutane and recycle isobutane) enter from the inlet of first fixed-bed reactor, olefin feed is divided into the inlet that n part enters the different fixing bed bioreactor respectively, and the beds that enters in first reactor after Trimethylmethane and the first part of olefin begins alkylated reaction; Exit at first reactor, alkene is by complete reaction, enter second beds in the reactor after remaining Trimethylmethane and second part of olefin, and the like, flow out n reactor until remaining Trimethylmethane and reaction product and enter fractionating system.
Embodiment
Below by drawings and Examples the present invention is further described, but content not thereby limiting the invention.
The isobutane feedstock of using in each embodiment and the Comparative Examples and the composition of olefin feedstock see Table 1.
Table 1
| Isobutane feedstock is formed (heavy %) | Olefin feedstock is formed (heavy %) | ||
| The anti-butylene impurity of propane iso-butane normal butane isobutene maleic: H2O S divinyl | 0.25 96.51 3.11 0.11 0.02 0.01 14ppm ＜0.2mg/m 3 ＜40ppm | The anti-butene-2 maleic-2 of propane normal butane iso-butane isobutene impurity: H2O S divinyl | 0.00 3.02 0.32 59.14 25.70 11.82 28ppm ＜1.0mg/m 3 ＜20ppm |
Among the embodiment, alkylation process is to overlap in the fixed bed reaction system that can adorn the 150ml catalyzer one to carry out.Reactive system is made up of following three parts:
(1), charging metering system: adopt two precision metering pumps (U.S. TSP company product), wherein a pump pumps into fixed-bed reactor with the Trimethylmethane material from the Trimethylmethane material pot.Another pump divides many branch roads to pump into beds different in the reactor in alkene from the olefin feed jar.Inlet amount is by the precise electronic balance under material pot metering, guaranteed stable, inlet amount accurately;
(2), reactive system: reactor can be adorned the 150ml catalyzer, with inert ceramic balls catalyzer is separated into a plurality of beds, and the population pipeline of alkene is all arranged in the upper end of each beds.The temperature homogeneous of the constant temperature zone assurance beds of process furnace and constant.The temperature of catalyst reactor bed is controlled by Britain West temperature control instrument.The pressure of reactor is controlled by high-accuracy pressure controller (U.S. Anaheim company product).Guaranteed the stable of temperature and pressure in the reactor and accurately;
(3), separation and analytical system: the reaction product of outflow reactor and unreacted material separate liquid-phase reaction product (alkylate oil) and the unreacted material of gas phase (Trimethylmethane and alkene) through high pressure and low pressure two-stage separator, unreacted material is by online gas-chromatography timing analysis, and alkylate oil regularly took out by an other stratographic analysis its full composition.
Analytical procedure: the composition that adopts Agilent-4890D (U.S. Agilent company product) gas-chromatography on-line analysis gas-phase product, chromatographic column is the OV-01 kapillary crosslinking column of 50m * 0.2mm, uses HP-5890 (hewlette-packard product) gas chromatographic analysis alkylate oil from C
3～C
2Full composition.Chromatographic column is the OV-01 capillary column of 50m * 0.2mm.
Embodiment 1
Preparation of catalysts: take by weighing 50.24g phospho-wolframic acid (H
3PW
12O
40.22H
2O, analytical pure, the Beijing Chemical Plant produces) be dissolved in the 350ml deionized water, be made into H
3PW
12O
40The aqueous solution.With the 180.5g granularity is the silica gel (SiO of 1.5mm
2, Haiyang Chemical Plant, Qingdao produces) and put into filter flask, handled 1.0 hours down 0.095 MPa vacuum tightness and 75 ℃, cool to room temperature, under the condition that keeps vacuum, add the H for preparing
3PW
12O
40Solution flooded 1.0 hours, then 100 ℃ of vacuum-dryings 4 hours, obtained containing 20 heavy %H
3PW
12O
40Carried heteropoly acid catalyst with 80 heavy % silica gel is designated as 20%H
3PW
12O
40/ SiO
2, the specific surface of catalyzer is 380m
2/ g (cryogenic nitrogen absorption BET method is measured).
The preparation method of other carried heteropoly acid catalyst is same as described above.
Take by weighing the above-mentioned 20%H of 10.0g
3PW
12O
40/ SiO
2Catalyzer, in the 150ml fixed-bed reactor of packing into, beds be that the inert ceramic balls of 1.5mm is separated with granularity up and down, constitute a beds.According to the alkane alkene ratio that needed reaction mass contacts with catalyzer, determine the quantity of beds.Filling second, the 3rd then uses the same method ... beds (referring to Fig. 1).Heat up, boost to the required temperature and pressure of alkylated reaction, pump into the Trimethylmethane material according to predetermined amount of flow to reactor with two precision metering pumps.By many branch roads the butylene material is pumped into the different catalysts bed simultaneously, begin to carry out alkylated reaction at reactor axial direction due different positions.
In the present embodiment, total mol ratio of isoparaffin and alkene is 15 in the setting reaction mass, and the catalyzer loading amount is 80 grams, is divided into 8 beds.According to the composition of Trimethylmethane in the table 1 and alkene, the flow that Trimethylmethane pumps into is 194.8 Grams Per Hours, and the flow that butylene pumps into is 12.4 Grams Per Hours, and the flow of total reaction material is 207.2 Grams Per Hours, and weight space velocity is 2.59 hours
-1The bed number of catalyst reactor is 8, and the alkene flow of each beds is 1.55 Grams Per Hours, and the isoparaffin and the olefin molar ratio of each beds are about 121, and other reaction conditions sees Table 2.
Reaction result sees Table 2.
Comparative Examples 1
This Comparative Examples explanation Trimethylmethane and the ratio I/O of alkene in fixed-bed reactor are that 15 reaction mass contacts the result who carries out Trimethylmethane and butene alkylation with catalyzer.
The catalyzer of 80 grams among the embodiment 1 packed in the 150ml reactor, as a beds.Trimethylmethane and butylene are pumped into reactor simultaneously, and the flow that Trimethylmethane pumps into is 194.8 Grams Per Hours, and the flow that butylene pumps into is 12.4 Grams Per Hours, and the flow of total reaction material is 207.2 Grams Per Hours, and weight space velocity is 2.59 hours
-1, the alkane alkene mol ratio that beds internal reaction material contacts with catalyzer is 15.Reaction conditions and the results are shown in table 2.
Embodiment 2
After embodiment 1 alkylated reaction carries out 1000 hours, temperature of reaction is dropped to 80 ℃, reaction pressure drops to 2.8MPa, and other reaction conditions is constant, and reaction result is listed in the table 2.
Embodiment 3
After embodiment 1 alkylated reaction carries out 1050 hours, temperature of reaction is raised to 180 ℃, reaction pressure is raised to 5.0MPa, and other reaction conditions is constant, and reaction result is listed in the table 2.
Table 2
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples 1 | ||
| Alkylation reaction condition | Temperature, ℃ | 140 | 80 | 180 | 140 |
| Pressure, MPa | 4.5 | 2.8 | 5.0 | 4.5 | |
| Weight space velocity, hour -1 | 2.59 | 2.59 | 2.59 | 2.59 | |
| Total alkane/alkene, mol ratio | 15.0 | 15.0 | 15.0 | 15.0 | |
| Alkane/alkene in the beds, mol ratio | 121 | 121 | 121 | 15.0 | |
| Sample time, hour | 1000 | 1050 | 1200 | 100 | |
| C ＝Olefin conversion, weight % | 100.0 | 100.0 | 100.0 | 100.0 | |
| The alkylate oil yield, g/g | 2.02 | 2.01 | 2.01 | 2.01 | |
| Distribution of reaction products, weight % C 5 C 6 C 7 C 8 C 9 + C 8 ＝The octane value RON MON of TMP/DMH alkylate oil | 3.78 4.11 5.33 82.37 4.41 0.00 7.01 96.5 94.6 | 3.42 4.02 5.18 82.82 4.56 0.00 7.23 96.8 94.5 | 3.58 4.46 6.08 80.99 4.89 0.00 7.00 96.6 94.3 | 3.65 5.05 6.56 74.77 9.97 0.00 5.21 92.8 90.7 | |
In the table 2, TMP is a trimethylpentane, DMH is a dimethylhexane, RON is a research octane number (RON), and MON is a motor-method octane number, and RON and MON value are according to document (Huston and Logan " Estimate AlkylYield and Quality ", hydrocarbon processing, in September, 1975,107-108 page or leaf) method is drawn by gas chromatographic analysis.
As can be seen from Table 2, the reaction mass of high alkane alkene ratio contacts the result who carries out alkylated reaction and compares with the alkylated reaction result (seeing Comparative Examples 1) of low alkane alkene ratio with catalyzer, the selectivity of the alkylated reaction of catalyzer is good, generate more purpose product-trimethylpentane, the octane value of alkylate oil is higher.
As can be seen from Table 2, when high alkane alkene contacts with solid acid alkylation catalysts when carrying out alkylated reaction than the reaction mass of (I/O:117), reaction is through after 1200 hours, catalyst activity (C
4Olefin conversion) remain on 100%, TMP/DMH mol ratio (the TMP/DMH molar ratio is represented the selectivity of catalyzer in alkylated reaction) reaches more than 7.00, and remains unchanged.
Embodiment 4
Take by weighing 50.24g silicotungstic acid (H
4SiW
12O
40.20H
2O, analytical pure, the Beijing Chemical Plant produces) be dissolved in the 350ml deionized water, be made into H
3PW
12O
40The aqueous solution.With the 180.5g granularity is the silica gel (SiO of 1.5mm
2, Haiyang Chemical Plant, Qingdao produces) and put into filter flask, handled 1.0 hours down 0.095 MPa vacuum tightness and 75 ℃, cool to room temperature, under the condition that keeps vacuum, add the H for preparing
3PW
12O
40Solution flooded 1.0 hours, then 100 ℃ of vacuum-dryings 4 hours, obtained containing 20 heavy %H
3PW
12O
40Carried heteropoly acid catalyst with 80 heavy % silica gel is designated as 20%H
4SiW
12O
40/ SiO
2, the specific surface of catalyzer is 376m
2/ g.
Press the method loading catalyst of embodiment 1, the catalyzer loading amount is 80 grams, is divided into 4 beds.Carry out alkylated reaction according to the listed reaction conditions of table 2 with the reactions steps identical with embodiment 1 with the alkylated reaction material shown in the table 1 then, the results are shown in Table 3 for gained.
Comparative Examples 2
The catalyzer of 80 grams among the embodiment 4 packed in the 150ml reactor, as a beds.Trimethylmethane and butylene are pumped into reactor simultaneously, and the flow that Trimethylmethane pumps into is 194.8 Grams Per Hours, and the flow that butylene pumps into is 12.4 Grams Per Hours, and the flow of total reaction material is 207.2 Grams Per Hours, and weight space velocity is 2.59 hours
-1, the alkane alkene mol ratio that beds internal reaction material contacts with catalyzer is 15.Reaction conditions and the results are shown in table 3.
Embodiment 5
Heteropolyacid salt C
S2.5H
0.5PW
12O
40Preparation: with 220.81gH
3PW
12O
40.21H
2O phospho-wolframic acid (chemical reagent factory of Beijing Xinhua product, analytical pure) and 20.85gC
S2CO
3(northern Tonghua factory products, analytical pure) is made into the solution of 0.35 and 0.87 volumetric molar concentration respectively by last stoichiometric equation weighing, under violent stirring, with C
S2CO
3Solution is added dropwise to H very lentamente
3PW
12O
40In the solution, CS
2CO
3After solution dropwises, continue to stir 30 minutes, then with the white precipitate that obtains 50 ℃ of dryings 24 hours, obtain C
S2.5H
0.5PW
12O
40.8H
2The O heteropolyacid salt.With the C for preparing
S2.5H
0.5PW
12O
40.8H
2O is levigate, and compressing tablet on tabletting machine is broken into small-particle then, sieves, and gets 10～20 purpose particles and is used for alkylated reaction as catalyzer.
Press the method loading catalyst of embodiment 1, the catalyzer loading amount is 80 grams, is divided into 12 beds.Carry out alkylated reaction according to the listed reaction conditions of table 2 with the reactions steps identical with embodiment 1 with the alkylated reaction material shown in the table 1 then, the results are shown in Table 3 for gained.
Comparative Examples 3
The catalyzer of 80 grams among the embodiment 5 packed in the 150ml reactor, as a beds.Trimethylmethane and butylene are pumped into reactor simultaneously, and the flow that Trimethylmethane pumps into is 194.8 Grams Per Hours, and the flow that butylene pumps into is 12.4 Grams Per Hours, and the flow of total reaction material is 207.2 Grams Per Hours, and weight space velocity is 2.59 hours
-1, the alkane alkene mol ratio that beds internal reaction material contacts with catalyzer is 15.Reaction conditions and the results are shown in table 3.
Table 3
| Embodiment 4 | Embodiment 5 | Comparative Examples 2 | Comparative Examples 3 | ||
| Alkylation reaction condition | Temperature, ℃ | 140.0 | 140.0 | 140.0 | 140.0 |
| Pressure, MPa | 4.5 | 4.5 | 4.5 | 4.5 | |
| Weight space velocity, hour -1 | 2.59 | 2.59 | 2.59 | 2.59 | |
| Total alkane/alkene, mol ratio | 15.0 | 15.0 | 15.0 | 15.0 | |
| Alkane/alkene in the beds, mol ratio | 60.6 | 181.7 | 15.0 | 15.0 | |
| Sample time, hour | 200 | 220 | 90 | 85 | |
| C ＝Olefin conversion, weight % | 100.0 | 100.0 | 100 | 100 | |
| The alkylate oil yield, g/g | 2.00 | 2.01 | 2.01 | 1.99 | |
| Distribution of reaction products, weight % C 5 C 6 C 7 C 8 C 9 + C 8 ＝ TMP/DMH | 3.22 4.34 5.97 82.23 4.24 0.00 6.18 | 3.38 4.69 6.34 78.62 6.97 0.00 6.48 | 3.48 4.50 6.12 74.65 11.25 0.00 4.78 | 3.02 4.88 6.89 72.46 12.75 0.00 4.21 | |
Embodiment 6
Present embodiment illustrates the reaction method (referring to Fig. 2) of a plurality of series connection fixed beds
The catalyzer identical 10 grams of in four placed in-line 50ml fixed-bed reactor, respectively packing into embodiment 1, heat up, boost to the required temperature and pressure of alkylated reaction, pump into Trimethylmethane material according to predetermined amount of flow to reactor with a precision metering pump, according to predetermined amount of flow the butylene material is pumped into the population of different reactor with another precision metering pump simultaneously, begin to carry out alkylated reaction.
Total alkane alkene of reaction mass is 22.3 than I/O, composition according to Trimethylmethane in the table 1 and olefin feed, the flow that the Trimethylmethane material pumps into is 97.4 Grams Per Hours, the flow that the butylene material pumps into each reactor is 1.05 Grams Per Hours, the flow of total reaction material is 101.6 Grams Per Hours, and weight space velocity is 2.54 hours
-1, each reactor inlet alkane alkene is about 89.4 (mol ratios) than I/O.Reaction conditions and the results are shown in table 4.
Comparative Examples 4
The catalyzer of 40 grams among the embodiment 1 packed in the 150ml reactor, as a beds.Trimethylmethane and butylene material are pumped into reactor simultaneously, and the flow that the Trimethylmethane material pumps into is 97.4 Grams Per Hours, and the flow that the butylene material pumps into is 4.2 Grams Per Hours, and the flow of total reaction material is 101.6 Grams Per Hours, and weight space velocity is 2.54 hours
-1, the alkane alkene mol ratio that beds internal reaction material contacts with catalyzer is 22.3.Reaction conditions and the results are shown in table 3.
Table 4
| Embodiment 6 | Comparative Examples 4 | ||
| Alkylation reaction condition | Temperature, ℃ | 140.0 | 140.0 |
| Pressure, MPa | 4.5 | 4.5 | |
| Weight space velocity, hour -1 | 2.54 | 2.54 | |
| Total alkane/alkene, mol ratio | 22.3 | 22.3 | |
| Alkane/alkene in the beds, mol ratio | 89.4 | 22.3 | |
| Sample time, hour | 150 | 150 | |
| C ＝Olefin conversion, weight % | 100.0 | 100 | |
| The alkylate oil yield, g/g | 2.01 | 2.00 | |
| Distribution of reaction products, weight % C 5 C 6 C 7 C 8 C 9 + C 8 ＝The octane value RON MON of TMP/DMH alkylate oil | 3.25 4.09 5.69 81.44 5.53 0.00 6.87 96.1 94.0 | 3.42 5.13 6.61 74.83 10.01 0.00 5.21 92.7 90.4 | |
Claims (12)
1. the solid acid alkylating process of isoparaffin and alkene, it is characterized in that in this method, total mol ratio of isoparaffin and alkene is 1～15 in the alkylated reaction raw material, alkene is divided into n part, isoparaffin order and the 1st is passed through solid acid catalyst to n part alkene under alkylation reaction condition, reclaim alkylate then, wherein, 2≤n≤34.
2. according to the process of claim 1 wherein that said isoparaffin is C
4To C
6, said alkene is C
3To C
6Singly-bound alkene.
3. according to the method for claim 2, wherein said isoparaffin is a Trimethylmethane, and said singly-bound alkene is iso-butylene, butene-1, butene-2 or its mixture.
4. according to the process of claim 1 wherein that said alkylation reaction condition is 10～350 ℃, 0.5～10.0MPa.
5. according to the method for claim 4, wherein alkylation reaction condition is that the emergent pressure of the critical temperature to 300 ℃ of said isoparaffin, said isoparaffin is to 10.0MPa.
6. according to the method for claim 1, it is characterized in that in alkylation reactor, said each part alkene being injected along the axial different positions place of solid acid catalyst bed.
7. according to the method for claim 1, it is characterized in that this method is to set up n placed in-line reactor, said each part alkene injected before each reactor.
8. according to the method for claim 6 or 7, isoparaffin is 15～500 with the mol ratio that each part alkene contacts at beds.
9. according to the method for claim 8, said isoparaffin is 60～300 with the mol ratio that each part alkene contacts at beds.
10. according to the method for claim 1, it is characterized in that alkene is divided into n part of five equilibrium.
11. according to the method for claim 6 or 7, said alkylation reactor is fixed-bed reactor.
12. according to the process of claim 1 wherein 4≤n≤20.
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| CN106431807A (en) * | 2016-05-06 | 2017-02-22 | 烟台大学 | Method for alkylation reaction of isobutane and butylene and system |
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| CN1059192C (en) * | 1997-11-24 | 2000-12-06 | 中国石油化工总公司 | Method for alkylation of isoalkanes and olefine |
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| CN106431807A (en) * | 2016-05-06 | 2017-02-22 | 烟台大学 | Method for alkylation reaction of isobutane and butylene and system |
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| CN110573594B (en) * | 2017-03-01 | 2022-10-25 | 雅宝欧洲有限责任公司 | Alkylation process with improved octane number |
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