CN1049418C - Method for alkylation of isomeric paraffine and olefine - Google Patents
Method for alkylation of isomeric paraffine and olefine Download PDFInfo
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Abstract
The present invention relates to a method for the alkylation of isomeric paraffine and olefine. In the method, under the condition of supercritical reaction, paraffine and olefine is in contact with a catalyst with a general formula of MxH[k-mx]YZ12O40*nH2O, wherein M is selected from one of alkali metal, ammonium, alkaline earth metal and IIIA group metal ions, Y is selected from one of phosphorus, silicon, germanium and arsenic atoms, Z is selected from one or two of tungsten and molybdenum atoms, k is 3 or 4, m is the valence of an M ion, x is greater than zero and is at most 4.0, mx is greater than zero and is at most 4.0, and n is a positive integer from 0 to 10. The method has the advantages of high conversion of olefine and high stability of catalyst activity.
Description
The invention relates to the addition method of stable hydrocarbon and unsaturated hydrocarbons, more specifically say so about the alkylation of isoparaffin and alkene.
As everyone knows, industrial be catalyzer with the vitriol oil or hydrofluoric acid, with isoparaffin, the isoparaffin and the alkene that particularly have lower molecular weight, the alkene that particularly has lower molecular weight carries out alkylated reaction and can prepare the alkane with higher molecular weight, particularly can prepare gasoline blend component with higher octane, but, adopt solid acid catalyst to replace the great research topic that sulfuric acid and hydrofluoric acid become a kind of inexorable trend and become this field because the vitriol oil and hydrofluoric acid has equipment intensive corrodibility and have problem such as serious environmental pollution.
In recent years, be used for existing much report of various new catalysts of abovementioned alkyl reaction, 557, US 3 as US 3,549,644,565, US 3,647, and 916, US 3,917,738, US 4,384,161 disclosed be the molecular sieve catalyst of active component with the molecular sieve; JP 01,245, and 853, US 3,962,133, US4,116,880, GB 1,432,720, GB 1,389,237 disclosed SO
4 2-Promoted super acidic catalyst; EP 0,433,954, US 3,678,120, US 3,852,371, WO 94/24075, US 3,855,342 disclosed liquid superacids or loading type Lewis acid catalyst etc., above-mentioned molecular sieve catalyst and solid super acid catalyst deactivation rate under common alkylation reaction condition is very fast, at several hours, even the dozens of minutes olefin conversion just is reduced to very low level from 100%, and the composition of alkylation reaction product is also undesirable, and problem and and unresolved etching problem to equipment that liquid superacid or loading type Lewis acid catalyst exist halogenide to run off.
WO 94/03415 discloses the alkylation of a kind of alkane and alkene, this method is included under the alkylation conditions, 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, adopt this method can improve the transformation efficiency of butylene and improved activity of such catalysts stability, but adopt this method olefin conversion still lower, butene conversion has only 86.3～99.4 heavy %.
CN 1,125,640A discloses a kind of Trimethylmethane and butene alkylated method, 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.According to example record, in batch reactor, carry out alkylated reaction, the alkylate oil yield is lower, can only reach 1.854 so that alkene (weight) is the highest, and increase with reaction times, catalyst activity descends rapidly, be that catalyst activity stability is lower, as record, with C according to the example 1
S2.5H
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 oil yield is 1.854, and 100 ℃ of oven dry are used down in similarity condition after 2 hours once more after the catalyst separating, and oily yield reduces to 1.384.
The objective of the invention is on the prior art basis, the higher isoparaffin of a kind of olefin conversion height and catalyst activity stability and the alkylation of alkene are provided.
The alkylation of isoparaffin provided by the invention and alkene is included in critical temperature and the reaction pressure that temperature of reaction is not less than isoparaffin in the reaction raw materials and is not less than under the condition of the emergent pressure of isoparaffin in the reaction raw materials, the reaction raw materials that will contain isoparaffin contacts with a kind of catalyzer with the reaction raw materials that contains alkene, and its key is that this catalyzer has following general formula:
M
xH
k-mxYZ
12O
40·nH
2O
Wherein M is selected from a kind of in alkalimetal ion, ammonium ion, alkaline-earth metal ions, the IIIA family metal ion; Y is selected from a kind of in phosphorus atom, Siliciumatom, germanium atom and the arsenic atom; Z is selected from one or both in tungsten atom, the molybdenum atom; K equals 3 or 4, and m is a M ionic valence state, and x is greater than zero any number between 4.0, and should satisfy 0＜mx≤4; N is 0～10 positive integer.
According to method provided by the invention, M in the described catalyzer can be selected from a kind of in alkalimetal ion, ammonium ion, alkaline-earth metal ions, the IIIA family metal ion, the preferred as alkali ion, a kind of in the ammonium ion, described alkalimetal ion refers to lithium, sodium, potassium, rubidium or cesium ion, described alkalimetal ion refers to beryllium, magnesium, calcium, strontium or barium ion, described IIIA family metal ion refers to aluminum ion, gallium ion, indium ion, thallium ion, the more preferred potassium ion of M ion, cesium ion, sodium ion or ammonium ion in the described catalyzer.
Y in the described catalyzer general formula is selected from a kind of in phosphorus atom, Siliciumatom, germanium atom, the arsenic atom, preferred phosphorus atom or Siliciumatom.
X in the described catalyzer general formula is greater than zero any number between 4.0, any number of any number between preferred 1.0～4.0 and satisfied 1≤mx≤4, more preferred 2.0～4.0, and satisfy 2≤mx≤4.
The described reaction raw materials that contains isoparaffin can be pure isoparaffin, also can contain other component that other does not influence alkylated reaction, and the concentration of isoparaffin in reaction raw materials can in very large range change, and isoparaffin can comprise C in theory
4Above various isoparaffins are considered the preferred C of this isoparaffin of industrial needs
4～C
6In the isoparaffin one or more are as Trimethylmethane, 2-methylbutane, 2-methylpentane, 3-methylpentane, 2,2-dimethylpentane etc., wherein more preferred Trimethylmethane.The reaction raw materials that contains alkene can be pure alkene, also can contain the component that other does not influence alkylated reaction, and the concentration of alkene in reaction raw materials can in very large range change, and alkene can comprise C in theory
3Above various monoene are considered the preferred C of this alkene of industrial needs
3～C
6In the monoene one or more, two strong positions in the described alkene are not required, as propylene, 1-butylene, 2-butylene, iso-butylene, 1-amylene, 2-amylene, 2-methyl-1-butene alkene, 2-methyl-2-butene, 3-methyl-1-butene, various hexenes etc., wherein more preferred propylene, butylene or its mixture.
The temperature of reaction that the invention provides method should be not less than the critical temperature of isoparaffin in the reaction raw materials, and preferred 135～400 ℃, more preferred 135～250 ℃; Reaction pressure should be not less than the emergent pressure of isoparaffin in the reaction raw materials, preferred 36～110 ℃ of normal atmosphere, more preferred 36～90 normal atmosphere.
The invention provides that the mol ratio of isoparaffin and alkene can be 2.0～100 in the method, preferred 10～90.The weight space velocity of reaction raw materials (WHSV) can be 0.1～20 hour
-1, preferred 0.5～8 hour
-1
The alkylated reaction of isoparaffin and alkene can carry out in various reactors, as fixed-bed reactor, intermittently tank reactor, moving-burden bed reactor, liquefied bed reactor or three-phase slurry bed reactor etc.
Method catalyst system therefor M provided by the invention
xH
3-mxYZ
12O
40NH
2O can prepare as follows:
(1) heteropolyacid that takes by weighing phosphorous, silicon, germanium or arsenic and the tungsten and/or the molybdenum of predetermined amount is made into quantitative water solution A.
(2) water-soluble salt that takes by weighing basic metal, ammonium, alkaline-earth metal ions or the IIIA family metal of predetermined amount is made into quantitative aqueous solution B.
(3) under violent stirring solution B slowly is added drop-wise in the solution A, adds the back and continue to stir 10～60 minutes, the precipitation that filtration and washing obtain 30～100 ℃ of oven dry, promptly gets method catalyst system therefor provided by the invention.
Compare with olefin alkylation process with the isoparaffin of solid acid as catalyst with existing, method provided by the invention has the advantage of olefin conversion height and catalyst activity good stability, for example, by method provided by the invention, 136 ℃ of temperature of reaction, reaction pressure 50 normal atmosphere, reaction raw materials weight space velocity 2.45 hours
-1, alkane alkene mol ratio 47.0 reaction conditions under, with C
S25H
0.5PW
12O
40For catalyzer carries out alkylated reaction with Trimethylmethane and butylene, butylene (C
4 =) transformation efficiency can reach 100 heavy %, the reaction operation was not fallen in 60 hours as follows, reaction product is formed with sulfuric acid process the time approaching, C
5Above alkane yield reaches 1.99～2.01 (butylene that gram/gram has transformed), approaches the theoretical value of 2.03 (gram/gram has transformed butylene), the transformation efficiency of butylene and C
5Above alkane yield is apparently higher than WO 94/03415 and CN 1125640A disclosed method; And (120 ℃ in critical temperature with below the pressure, 30 normal atmosphere) adopt same catalyzer and reaction raw materials, when carrying out Trimethylmethane and butene alkylation under close condition, turning round, butene conversion descends catalyzer rapid deactivation (as shown in Figure 1) fast after 40 hours.Method provided by the invention in addition also has not etching apparatus, advantage free from environmental pollution.
Fig. 1 is C
S2.5H
0.5PW
12O
40During for catalyzer, adopt under method provided by the invention and the subcritical reaction conditions Trimethylmethane and butylene to carry out the alkylated reaction butene conversion and scheme over time.
The following examples will the present invention will be further described, but not thereby limiting the invention.
The composition of used isoparaffin of alkylated reaction and olefin feedstock is listed in the table 1 in the example.
Table 1
| The reaction raw materials that contains Trimethylmethane | The reaction raw materials that contains butylene | ||
| Component | Content, heavy % | Component | Content, heavy % |
| Propane Trimethylmethane normal butane butylene | 1.82 94.85 2.21 1.12 | Just, the trans 2-butylene of isomery butylene normal butane cis 2-butylene | 2.92 11.62 57.70 27.76 |
Comparative Examples 1
With the vitriol oil is the alkylated reaction that catalyzer carries out Trimethylmethane and butylene.
Take by weighing 73.3 grams, 95 heavy % sulfuric acid (analytical pure, Beijing Lee satisfies the chemical plant and produces) add in the high pressure tank reactor, 10 ℃ of temperature of reaction, add 18.0 grams under reaction pressure 7.0MPa and the violent stirring and contain the reaction raw materials of Trimethylmethane and the reaction raw materials that 3.48 grams contain butylene, reacted 2 hours, form with the gas phase in the SP-3420 gas chromatograph analytical reaction still, chromatographic column is an OV-01 kapillary crosslinking column, with the phase composite of HP-5890 gas chromatograph analytic liquid, chromatographic column is the OV-01 capillary column, the composition of reaction raw materials is listed in the table 1, and reaction conditions and reaction result are listed in the table 3.
Example 1
Carry out the alkylated reaction of Trimethylmethane and butylene by method provided by the invention.
With 22.81 gram phospho-wolframic acid (H
3PW
12O
4021H
2O, analytical pure, chemical reagent factory of Beijing Xinhua produces) and 2.85 gram Cs
2CO
3(analytical pure, northern Tonghua factory produces) adds the solution that water is made into 0.35 and 0.87 mol respectively, under violent stirring with Cs
2CO
3Solution slowly is added drop-wise in the Salkowski's solution, and reaction is carried out (M is Cs, x=2.5) here by formula (I).
Take by weighing 10.0 gram Cs
2.5H
0.5PW
12O
40(butt) packs in 25 milliliters of fixed-bed reactor, feed nitrogen gas stream, heat up, boost to temperature required and pressure, and kept 16 hours, with two precision metering pumps (U.S. Eldex Lab., Inc. company produce) respectively predetermined amounts pump into the reaction raw materials that contains Trimethylmethane and butylene, with SP-3420 gas chromatograph timing analysis reaction end gas, and regularly taking out product liquid analyzes its composition with the HP-5890 gas chromatograph, and reaction raw materials is formed with table 1, and table 2 has provided C in the reaction raw materials
4The critical temperature of hydro carbons and emergent pressure (selecting from CRC Handbook of Chemistry and physics, Editor, R.C.Weast andD.R.Lide, 1990), reaction conditions and reaction result are listed in the table 3.(▲ shown in straight line) then shows C among Fig. 11
4 =Transformation efficiency is schemed over time.
The presentation of results of table 3, the butene conversion and the product that the invention provides method distribute near the sulfuric acid process of industrial extensive employing, C
5 +Yield can reach the C that 2.00 gram/grams have transformed
4 =The C that has transformed near 2.03 gram/grams
4 =Theoretical value, and method provided by the invention does not exist equipment corrosion and environmental pollution problems.
Table 2
| C 4Hydro carbons | Critical temperature ℃ | Emergent pressure, normal atmosphere |
| Trimethylmethane | 135.0 | 35.9 |
| Normal butane | 152.0 | 37.5 |
| 1-butylene | 146.4 | 39.7 |
| Trans 2-butylene | 160.0 | 40.5 |
| The cis 2-butylene | 155.0 | 41.5 |
| Iso-butylene | 144.7 | 40.7 |
Table 3
| Catalyzer | Cs 2.5H 0.5PW 12O 40 | 95% sulfuric acid | ||||||
| Temperature of reaction, ℃ | 136.0 | 10.0 | ||||||
| Reaction pressure, normal atmosphere | 50.0 | 7.0 | ||||||
| Alkane alkene mol ratio | 47.0 | 6.0 | ||||||
| Weight space velocity, hour -1 | 2.45 | - | ||||||
| Reaction times, hour | 6 | 10 | 24 | 32 | 48 | 52 | 60 | 2 |
| C ＝ 4Transformation efficiency, heavy % | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| C + 5The C that yield gram/gram has transformed ＝ 4 | 2.00 | 1.99 | 2.02 | 1.97 | 1.99 | 1.97 | 1.98 | 2.00 |
| C 5 +Product distributes, heavy % C 5C 6C 7C 8C 9 +C ＝ 8TMP/DMHx | 3.17 0.93 1.86 63.94 30.10 0.00 2.2 | 1.67 0.61 1.52 64.10 32.10 0.00 2.0 | 1.72 0.82 2.36 65.40 29.70 0.00 2.2 | 1.80 0.92 2.87 63.61 30.80 0.00 2.1 | 0.20 1.10 2.80 63.87 31.40 0.00 2.6 | |||
*TMP/DMH is the mol ratio (down together) of trimethylpentane and dimethylhexane
Comparative Examples 2
This Comparative Examples illustrates that method provided by the invention is better than prior art
Carry out the alkylated reaction of Trimethylmethane and butylene at isoparaffin critical temperature and the reaction conditions below the pressure, catalyzer and consumption thereof, reaction raw materials, reaction unit be with example 1, and just reaction conditions is 120 ℃ of temperature of reaction, reaction pressure 30.0 normal atmosphere, alkane alkene mol ratio 45.5, weight space velocity 2.35 hours
-1, reaction conditions and reaction result are shown in Table 4, butene conversion with the variation in reaction times shown in 2 (curves shown in the △) among Fig. 1.
The result of Fig. 1 shows, adopt method provided by the invention, butene conversion can reach 100 heavy %, and 60 hours butene conversion of reaction operation are not fallen as follows, and under the condition that is lower than Trimethylmethane critical temperature and pressure, carry out same reaction, move that butene conversion descends the catalyzer rapid deactivation fast after 40 hours.
As can be seen at the alkylated reaction of Trimethylmethane critical temperature and Trimethylmethane that carries out below the pressure and butylene, move after 40 hours C from the result of table 4
+ 5Yield drops to 1.41 gram/grams from about 2.00 gram/grams, this explanation this moment has a large amount of alkene oligomerizations reactions take place, and compares explanation with the result of table 3, and method provided by the invention is better than prior art.
Table 4
| Catalyzer | Cs 2.5H 0.5PW 12O 40 | ||||||
| Temperature of reaction, ℃ | 120℃ | ||||||
| Reaction pressure, normal atmosphere | 30.0 | ||||||
| Alkane alkene mol ratio | 45.5 | ||||||
| Weight space velocity, hour -1 | 2.35 | ||||||
| Reaction times, hour | 4 | 8 | 24 | 40 | 48 | 50 | 52 |
| C 4 ＝Transformation efficiency, heavy % | 100 | 100 | 100 | 100 | 87.8 | 81.2 | 72.4 |
| C 5 +The C that yield gram/gram has transformed 4 ＝ | 2.00 | 1.97 | 1.96 | 1.97 | 1.84 | 1.70 | 1.41 |
| C + 5Product distributes, heavy % C 5C 6C 7C 8C + 9C 8 ＝TMP/DMH | 0.52 0.75 2.03 63.30 33.40 0.00 2.1 | 1.02 2.47 2.20 62.11 32.20 0.00 1.9 | 0.39 0.72 1.74 58.30 31.96 6.89 1.7 | 0.42 0.89 2.01 49.80 36.40 10.48 1.4 | |||
Example 2
Carry out the alkylated reaction of Trimethylmethane and butylene by method provided by the invention.
Reaction unit, reaction raw materials, catalyzer and consumption thereof are with example 1, it is the reaction conditions difference, the starting temperature of reaction and pressure are respectively 136.0 ℃ and 50 normal atmosphere, reaction temperature-resistant raising reaction pressure to 80 normal atmosphere of maintenance after 10 hours, continue reaction to 32 hours, reduce reaction pressure to 50 normal atmosphere, temperature of reaction is increased to 200 ℃ simultaneously, continues reaction, reduce temperature of reaction to 136 ℃ then to 48 hours.Other conditions and the reaction result of reaction are listed in the table 5.
The result of table 5 shows that method provided by the invention can be carried out in the condition that is higher than isoparaffin critical temperature and pressure, and its temperature of reaction and pressure can be in changes in a big way.
Table 5
| Catalyzer | Cs 2.5H 0.5PW 12O 40 | |||
| Temperature of reaction, ℃ | 136.0 | 136.0 | 200.0 | 136.0 |
| Reaction pressure, | 50 | 80 | 50 | 50 |
| Alkane alkene mol ratio | 47.0 | 47.0 | 47.0 | 47.0 |
| Weight space velocity, hour -1 | 2.45 | 2.45 | 2.45 | 2.45 |
| Reaction times, | 10 | 32 | 48 | 65 |
| C ＝ 4Transformation efficiency, heavy % | 100 | 100 | 100 | 100 |
| C + 5The C that yield gram/gram has transformed 4 ＝ | 2.01 | 2.00 | 2.02 | 1.99 |
| C + 5Product distributes, heavy % C 5C 6C 7C 8C + 9C ＝ 8TMP/DMH | 1.78 0.75 1.64 65.74 30.09 0.00 2.2 | 2.14 0.82 1.83 67.41 27.80 0.00 2.1 | 1.89 0.91 2.05 64.83 30.32 0.00 2.2 | 1.84 0.87 2.14 66.28 28.87 0.00 2.1 |
Example 3
Carry out the alkylated reaction of Trimethylmethane and butylene according to method provided by the invention.
Reaction unit, reaction raw materials, catalyzer and consumption thereof are the reaction conditions difference with example 1, and initial alkane alkene mol ratio is 47.0, and the starting weight air speed is 2.45 hours
-1, reduce air speed to 1.05 hour after reaction proceeds to 24 hours
-1, improve air speed to 6.15 hour after reaction proceeds to 32 hours
-1, reaction reduces air speed to 2.45 hour after proceeding to 40 hours simultaneously
-1And reducing alkane alkene mol ratio to 21.5, reaction proceeds to 48 hours
-1Keep the constant raising alkane of air speed alkene mol ratio to 85.0 later on, react and reduce alkane alkene mol ratio to 47.0 after 56 hours, reaction conditions and reaction result are listed in the table 6.
The result of table 6 shows that the invention provides the alkane alkene mol ratio of method and the weight space velocity of reaction raw materials can change in a big way.
Table 6
| Catalyzer | Cs 2.5H 0.5PW 12O 40 | |||||
| Temperature of reaction, ℃ | 136.0 | 136.0 | 136.0 | 136.0 | 136.0 | 136.0 |
| Reaction pressure, | 50 | 50 | 50 | 50 | 50 | 50 |
| Alkane alkene mol ratio | 47.0 | 47.0 | 47.0 | 21.5 | 85.0 | 47.0 |
| Weight space velocity, hour -1 | 2.45 | 1.05 | 6.15 | 2.45 | 2.45 | 2.45 |
| Reaction times, hour | 24 | 32 | 40 | 48 | 56 | 75 |
| C 4 ＝Transformation efficiency, heavy % | 100 | 100 | 100 | 100 | 100 | 100 |
| C 5 +The C that yield gram/gram has transformed 4 ＝ | 2.02 | 2.00 | 2.01 | 1.99 | 2.00 | 2.00 |
| C 5 +Product distributes, heavy % C 5C 6C 7C 8C 9 +C 8 ＝TMP/DMH | 1.75 0.84 1.72 66.21 29.48 0.00 2.0 | 2.11 1.42 2.32 68.94 25.21 0.00 2.3 | 1.52 0.65 1.64 62.59 33.60 0.00 2.0 | 1.67 0.79 1.84 64.15 31.55 0.00 2.1 | 2.35 1.52 2.67 68.41 25.06 0.00 2.4 | 1.65 0.92 1.94 65.83 29.66 0.00 2.2 |
Example 4
Carry out the alkylated reaction of Trimethylmethane and butylene according to method provided by the invention.
Take by weighing 91.23 gram phospho-wolframic acids (with example 1) and 5.80 gram K
2CO
3(analytical pure, Deneb Tonghua factory produce) adds 80 milliliters in water and 70 milliliters respectively and is made into two kinds of solution, under violent stirring with K
2CO
3Solution slowly is added drop-wise in the Salkowski's solution, the reaction by formula (I) carry out (M is K here, x=3.0), K
2CO
3Solution dropwises the back and continue to stir 30 minutes, filters and precipitates with 20 times of distilled water washs, and in 50 ℃ of dryings 24 hours, the product that obtains was K
3PW
12O
408H
2O is with the K for preparing
3PW
12O
408H
2O is levigate, compression molding, and broken then, sieve is got 20～40 purpose particles and is promptly got method catalyst system therefor provided by the invention.
Adopt 10.0 gram K
3PW
12O
408H
2O (butt) was a catalyzer, uses reaction unit, the reaction raw materials identical with example 1,136.0 ℃ of temperature of reaction, reaction pressure 50.0 normal atmosphere, alkane alkene mol ratio 47.1 and weight space velocity 2.44 hours
-1Condition under carry out the alkylation reaction of Trimethylmethane and butylene, reaction conditions and reaction result are listed in the table 7.
Table 7
| Catalyzer | K 3.0PW 12O 40 | ||||||
| Temperature of reaction, ℃ | 136.0 | ||||||
| Reaction pressure, normal atmosphere | 50.0 | ||||||
| Alkane alkene mol ratio | 47.1 | ||||||
| Weight space velocity, hour -1 | 2.44 | ||||||
| Reaction times, hour | 4 | 10 | 24 | 40 | 60 | 80 | 100 |
| C 4 ＝Transformation efficiency, heavy % | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| C 5 +The C that yield gram/gram has transformed 4 ＝ | 2.00 | 1.99 | 1.98 | 1.98 | 1.99 | 1.97 | 1.96 |
| C 5 +Product distributes, heavy % C 5C 6C 7C 8C 9 +C 8 ＝TMP/DMH | 0.72 0.84 1.85 63.12 33.47 0.00 2.1 | 0.78 1.02 2.08 62.51 33.61 0.00 2.0 | 0.88 0.99 1.99 61.30 34.84 0.00 1.9 | 0.92 1.11 2.11 62.80 33.06 0.00 1.8 | 0.85 1.00 2.24 60.89 35.02 0.00 1.9 | ||
Example 5
Carry out the alkylated reaction of Trimethylmethane and butylene by method provided by the invention.
With 34.10 gram phospho-molybdic acid (H
3PMo
12O
4017H
2O, analytical pure, chemical reagent factory of Beijing Xinhua produces) and 6.52 gram Cs
2CO
3(with example 1) adds 30 milliliters in water and 70 milliliters respectively and is made into two kinds of solution, under violent stirring with Cs
2CO
3Solution slowly is added drop-wise in the molybdophosphate solution, and reaction is carried out (M is Cs, x=2.5) here by formula (II).
Adopt 10.0 gram Cs
2.5H
0.5PMo
12O
40(butt) is catalyzer, uses reaction unit, the reaction raw materials identical with example 1,136.0 ℃ of temperature of reaction, and reaction pressure 50.0 normal atmosphere, alkane alkene mol ratio 47.5 and weight space velocity 2.45 hours
-1Condition under carry out the alkylated reaction of Trimethylmethane and butylene, reaction conditions and reaction result are listed in the table 8.
Table 8
| Catalyzer | Cs 2.5H 0.5PMo 12O 40 | ||||
| Temperature of reaction, ℃ | 136.0 | ||||
| Reaction pressure, normal atmosphere | 50.0 | ||||
| Alkane alkene mol ratio | 47.5 | ||||
| Weight space velocity, hour -1 | 2.45 | ||||
| Reaction times, hour | 4 | 16 | 24 | 48 | 56 |
| C
4 ＝Transformation efficiency, | 100 | 100 | 100 | 100 | 100 |
| C 5 +The C that yield gram/gram has transformed 4 ＝ | 1.97 | 1.96 | 1.98 | 1.99 | 1.96 |
| C 5 +Product distributes, heavy % C 5C 6C 7C 8C 9 +C 8 ＝TMP/DMH | 0.74 1.84 1.98 53.02 42.42 0.00 1.8 | 0.68 1.62 2.18 51.11 44.41 0.00 1.7 | 0.64 1.52 1.87 50.41 45.56 0.00 1.6 | 0.75 1.40 2.21 50.89 44.75 0.00 1.6 | |
Example 6
Carry out the alkylated reaction of Trimethylmethane and butylene according to method provided by the invention.
Take by weighing 34.64 gram silicotungstic acid (H
4SiW
12O
4015H
2O, analytical pure, reagent two factories in Shanghai produce) and 4.48 gram Cs
2CO
3(with example 1) adds 30 milliliters in water and 50 milliliters of wiring solution-formings respectively, under violent stirring with Cs
2CO
3Solution slowly is added drop-wise in the tungstosilicic acid solution, and reaction is carried out (M is Cs, x=2.5) here by formula (III).
Adopt 10.0 gram Cs
2.5H
1.5SiW
12O
40(butt) is catalyzer, uses reaction unit, the reaction raw materials identical with example 1,136.0 ℃ of temperature of reaction, and reaction pressure 50.0 normal atmosphere, alkane alkene mol ratio 47.7 and weight space velocity 2.44 hours
-1Condition under carry out the alkylated reaction of Trimethylmethane and butylene, reaction conditions and reaction result are listed in the table 9.
Table 9
| Catalyzer | Cs 2.5H 1.5SiW 12O 40 | |||||
| Temperature of reaction, ℃ | 136.0 | |||||
| Reaction pressure, normal atmosphere | 50.0 | |||||
| Alkane alkene mol ratio | 47.7 | |||||
| Weight space velocity, hour -1 | 2.44 | |||||
| Reaction times, hour | 4 | 12 | 24 | 48 | 56 | 74 |
| C
4 ＝Transformation efficiency, | 100 | 100 | 100 | 100 | 100 | 100 |
| C 5 +The C that yield gram/gram has transformed 4 ＝ | 1.92 | 1.90 | 1.88 | 1.91 | 1.87 | 1.85 |
| C 5 +Product distributes, heavy % C 5C 6C 7C 8C 9 +C 8 ＝TMP/DMH | 0.51 1.37 1.18 52.41 44.53 0.00 1.9 | 0.48 1.22 1.23 52.20 44.87 0.00 1.6 | 0.54 1.07 1.13 50.85 46.41 0.00 1.6 | 0.35 1.51 1.28 50.32 46.54 0.00 1.5 | 0.27 0.89 1.05 48.53 49.26 0.00 1.4 | |
Claims (9)
1. the alkylation of isoparaffin and alkene, being included in critical temperature and the reaction pressure that temperature of reaction is not less than isoparaffin in the reaction raw materials is not less than under the condition of isoparaffin emergent pressure in the reaction raw materials, the reaction raw materials that will contain isoparaffin contacts with a kind of catalyzer with the reaction raw materials that contains alkene, it is characterized in that this catalyzer has following general formula:
M
xH
K-mxYZ
12O
40NH
2O wherein M is selected from a kind of in alkalimetal ion, ammonium ion, alkaline-earth metal ions and the IIIA family metal ion, and Y is selected from a kind of in phosphorus atom, Siliciumatom, germanium atom and the arsenic atom; Z is selected from one or both in tungsten atom, the molybdenum atom, and k is 3 or 4, and m is the valence state of M metal ion, and x is greater than zero any number between 4.0, and should satisfy 0＜mx≤4; N is 0～10 positive integer; Described isoparaffin refers to C
4～C
6Isoparaffin, alkene refers to C
3～C
6Singly-bound alkene.
2. according to the described method of claim 1, it is characterized in that the M in the described catalyzer general formula is selected from potassium ion, cesium ion, sodium ion or ammonium ion.
3. according to the described method of claim 1, it is characterized in that the Y in the described catalyzer general formula is selected from phosphorus atom or Siliciumatom.
4. according to the described method of claim 1, it is characterized in that the M in the described catalyzer general formula is selected from potassium ion or cesium ion; Y is selected from phosphorus atom or Siliciumatom.
5. according to the described method of claim 1, it is characterized in that described isoparaffin refers to Trimethylmethane, alkene is selected from propylene, butylene or its mixture.
6. according to the described method of claim 1, the processing condition that it is characterized in that this method are that temperature of reaction is 135～400 ℃, and reaction pressure is 36～110 normal atmosphere, and the mol ratio of isoparaffin and alkene is 2.0～100, and the reaction raw materials weight space velocity is 0.1～20 hour
-1
7. according to the described method of claim 6, it is characterized in that described temperature of reaction is 135～250 ℃, reaction pressure is 36～90 normal atmosphere, and the mol ratio of isoparaffin and alkene is 10～90, and the reaction raw materials weight space velocity is 0.5～8 hour
-1
8. according to the described method of claim 1, it is characterized in that the x in the described catalyzer general formula is any number between 1.0～4.0 and satisfies 1≤mx≤4.
9. described according to Claim 8 method is characterized in that described x is any number of 2.0～4.0 and satisfies 2≤mx≤4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96120999A CN1049418C (en) | 1996-12-11 | 1996-12-11 | Method for alkylation of isomeric paraffine and olefine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96120999A CN1049418C (en) | 1996-12-11 | 1996-12-11 | Method for alkylation of isomeric paraffine and olefine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1184797A CN1184797A (en) | 1998-06-17 |
| CN1049418C true CN1049418C (en) | 2000-02-16 |
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ID=5126728
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96120999A Expired - Lifetime CN1049418C (en) | 1996-12-11 | 1996-12-11 | Method for alkylation of isomeric paraffine and olefine |
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| Country | Link |
|---|---|
| CN (1) | CN1049418C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1100028C (en) | 1999-07-22 | 2003-01-29 | 中国石油化工集团公司 | Isoalkane and alkylation method of olefine |
| CN1291954C (en) | 2004-01-19 | 2006-12-27 | 中国石油化工股份有限公司 | Akylation reaction method for solid acid catalyzed isomeric paraffine and olefins |
| CN103801242B (en) * | 2012-11-03 | 2015-12-02 | 中国石油化工股份有限公司 | Reactor and the alkylation reaction method utilizing this reactor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1057641A (en) * | 1990-06-23 | 1992-01-08 | 美孚石油公司 | Isoparaffin-olefin alkylation process |
| CN1125640A (en) * | 1994-12-28 | 1996-07-03 | 中国石油化工总公司 | Isobutane and butene alkylated solid heteropoly acid salt catalyzer |
-
1996
- 1996-12-11 CN CN96120999A patent/CN1049418C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1057641A (en) * | 1990-06-23 | 1992-01-08 | 美孚石油公司 | Isoparaffin-olefin alkylation process |
| CN1125640A (en) * | 1994-12-28 | 1996-07-03 | 中国石油化工总公司 | Isobutane and butene alkylated solid heteropoly acid salt catalyzer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1184797A (en) | 1998-06-17 |
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