CN104829407A - Method for preparing 2,3-dimethyl-1-butylene through gas-solid phase isomerization catalysis - Google Patents

Abstract

The purpose of the invention is providing a method for preparing 2,3-dimethyl-1-butylene through gas-solid phase isomerization catalysis. The method is characterized in that highly pure tetramethyl ethylene DMB-2 undergoes a gas phase isomerization reaction at a certain temperature with a Na-Y molecular sieve as a catalyst to form DMB-1, the gas phase isomerization reaction temperature is 110-130DEG C, and the raw material gasification temperature is 120-140DEG C. The method provides reliable production process conditions for large scale production of 2,3-dimethyl-1-butylene.

Description

The method of 2,3-dimethyl-1-butylene is prepared in the isocatalysis of a kind of gas-solid phase

Technical field

The present invention relates to the method that 2,3-dimethyl-1-butylene is prepared in the isocatalysis of a kind of gas-solid phase.

Background technology

In recent years, due to the great development in spices market, tonalide spices (Tonalide), as daily type spices, is internationally recognized use safety, and a kind of very good fixative harmless to human skin, its development prospect is long-range.DMB-1 (2,3-dimethyl-1-butylene), as the intermediate of synthesis " Tonalide ", is developed rapidly, neohexene (3 is replaced with DMB-1,3-dimethyl-1-butylene) produce " Tonalide " spices, there is cost low, the advantages such as steady quality.

Summary of the invention

The isocatalysis of a kind of gas-solid phase is the object of the present invention is to provide to prepare 2; the method of 3-dimethyl-1-butylene; the method utilizes highly purified tetramethyl-ethylene (DMB-2; 2; 3-dimethyl-2-butylene) be raw material; adopt Na-Y molecular sieve to be that catalyzer carries out gas phase isomerization reaction at a certain temperature, make DMB-2 tautomerize to DMB-1, for large-scale production 2.3-dimethyl-1-butylene provides reliable manufacturing condition.

The present invention specifically provides the isocatalysis of a kind of gas-solid phase and prepares 2, the method of 3-dimethyl-1-butylene, it is characterized in that: take tetramethyl-ethylene as raw material, Na-Y molecular sieve is adopted to be that catalyzer carries out gas phase isomerization reaction, finally prepare 2,3-dimethyl-1-butylene, wherein gas phase isomerization reaction temperature is at 110-130 DEG C, and the gasification temperature of raw material is at 120-140 DEG C.

Gas-solid phase of the present invention isocatalysis prepares 2, the method of 3-dimethyl-1-butylene, it is characterized in that: the gas flow rate entering reactor feedstocks is the key factor affecting isomerization reaction, it is best for controlling gas flow rate at 7.5 ~ 12cm/s, under this flow velocity, transformation efficiency is 10 ~ 18%, and selectivity is more than 95%.Lower than this flow velocity, the selection of DMB-1, lower than 95%, is unfavorable for reaction; When gas speed is greater than 12cm/s, the transformation efficiency of DMB-2 is very low, and the growing amount of superpolymer does not reduce simultaneously, thus the selectivity of DMB-1 is reduced.

The method of 2,3-dimethyl-1-butylene is prepared in gas-solid phase of the present invention isocatalysis, it is characterized in that: before reaction, raw material tetramethyl-ethylene needs drying, makes its water content reduce to 60-100ppm, thus the work-ing life of extending catalyst greatly.

The method of 2,3-dimethyl-1-butylene is prepared in gas-solid phase of the present invention isocatalysis, it is characterized in that, optimal processing parameter: gas flow rate is 10.3cm/s, the water content of tetramethyl-ethylene is 115ppm.

Gas-solid phase of the present invention isocatalysis prepares 2, the method of 3-dimethyl-1-butylene, it is characterized in that, raw material tetramethyl-ethylene take propylene as raw material, be catalyst dimerization of propylene with two (tricyclohexyl phosphine) Nickel Chloride, through two to aggregate into, in cut, isomery, rectifying separation obtain tetramethyl-ethylene, concrete preparation process is as follows:

1), prepare two (tricyclohexyl phosphine) Nickel Chloride toluene homogeneous phase solution and aluminum alkyls toluene homogeneous phase solution, wherein aluminum alkyls is sesquialter aluminium, is selected from diethyl aluminum chloride and/or ethylaluminum dichloride;

2), dipolymer reactor is shell and tube heat exchanger form, heat interchanging area 40m ²; Shell leads to cold, and sets temperature of reactor as-10 ~ 0 DEG C;

3), liquid propene flows through water cooler, and water cooler design temperature is-10 ~ 0 DEG C; Enter shell and tube reactor, add propylene 500L;

4) reactor cycles pump (canned-motor pump Q=15m, is started ³/ hr), propylene feedstocks self-circulation is in reactor;

5), the aluminum alkyls toluene homogeneous phase solution of 1 ~ 2L concentration to be two (tricyclohexyl phosphine) Nickel Chloride toluene homogeneous phase solution and 0.10 ~ 0.30L concentration of 0.05 ~ 1wt% be 10 ~ 20wt% presses volume pump to pump into shell-and-tube reactor in warp respectively;

6), at above-mentioned canned-motor pump Q=15m ³under the circulation promotion of/hr, there is dimerization reaction, control pressure 0.6 ~ 0.0MPa;

7), reaction residual voltage is under 0.0MPa, and continue reaction 30min, off-response device shielding recycle pump leads to the circulation valve of reactor, opens the arm valve leading to inactivation still simultaneously, carries out the process of water inactivation to reactant;

8), after inactivation dipolymer oil phase is after aqueous phase washing, and oil phase merges and obtains propylene dimer organic phase, through in cut, isomery, rectifying separation obtain 2,3-neohexene.

Wherein, the preparation method of described two (tricyclohexyl phosphine) Nickel Chloride toluene homogeneous phase solution is:

1, take chlorocyclohexane as raw material, after grignard reaction, carry out phosphating reaction with phosphorus trichloride, generate thricyclohexyl phosphorus ligand, thricyclohexyl phosphorus ligand and six water nickelous chloride complexings, obtained two (tricyclohexyl phosphine) Nickel Chloride after refining;

Its molecular formula: C ₃₆h ₆₆cl ₂niP ₂

Molecular weight: 690.46.

2, be that the industrial toluene of 300 ~ 500ppm pumps in the drying tower filling 3A molecular sieve by water content, control the residence time 16 ~ 32hr and carry out drying treatment, make its water content reach 50 ~ 100ppm; Dried toluene is pumped into 0.5m ³in catalyst preparation still, under stirring, add two (tricyclohexyl phosphine) Nickel Chloride of powdery from feed hopper place, stirred at ambient temperature extremely dissolves completely, in burgundy solution, and two (tricyclohexyl phosphine) Nickel Chloride concentration 0.1 ~ 1wt%.

Accompanying drawing explanation

Fig. 1 experimental installation structure diagram (wherein, 1, producer gas generator, 2, gas preheater, 3, tubular reactor, 4, condenser, 5, receiving bottle, 6, thermometer).

Fig. 2 time/transformation efficiency/selectivity graph of a relation.

Embodiment

1), two (tricyclohexyl phosphine) Nickel Chloride toluene homogeneous phase solution of preparation and aluminum alkyls toluene homogeneous phase solution, wherein aluminum alkyls is sesquialter aluminium, is selected from diethyl aluminum chloride and/or ethylaluminum dichloride (chlorine/al mole ratio is 1.0 ~ 2.0);

2), dipolymer reactor is shell and tube heat exchanger form, heat interchanging area 40m ²; Shell leads to cold, and sets temperature of reactor as-10 ~ 0 DEG C;

3), liquid propene flows through water cooler, and water cooler design temperature is-10 ~ 0 DEG C; Enter shell and tube reactor, add propylene 500L;

4) reactor cycles pump (canned-motor pump Q=15m, is started ³/ hr), propylene feedstocks self-circulation is in reactor;

5), the aluminum alkyls toluene homogeneous phase solution of 1 ~ 2L concentration to be two (tricyclohexyl phosphine) Nickel Chloride toluene homogeneous phase solution and 0.10 ~ 0.30L concentration of 0.05 ~ 1wt% be 10 ~ 20wt% presses volume pump to pump into shell-and-tube reactor in warp respectively;

6), at above-mentioned canned-motor pump Q=15m ³under the circulation promotion of/hr, there is dimerization reaction, control pressure 0.6 ~ 0.0MPa;

7), reaction residual voltage is under 0.0MPa, and continue reaction 30min, off-response device shielding recycle pump leads to the circulation valve of reactor, opens the arm valve leading to inactivation still simultaneously, carries out the process of water inactivation to reactant;

8), after inactivation dipolymer oil phase through aqueous phase washing after, oil phase merges and obtains propylene dimer organic phase, cut in warp, (product comprises 2,3-dimethyl-1-butylene and 2 to obtained 2, the 3-neohexene of isomery, rectifying separation, 3-dimethyl-2-butylene, be referred to as 2,3-neohexene, adopt 2 wherein, 3-dimethyl-2-butylene is that high purity 2,3-dimethyl-1-butylene prepared further by raw material).

9), quantitative catalyzer (Na-Y molecular sieve) is loaded in tubular reactor 3.

10), as shown in Figure 1, producer gas generator 1, gas preheater 2, tubular reactor 3, condenser 4, receiving bottle 5 and pump of constant delivery type are connected and installed successively.

11), by tubular reactor 3, gas preheater 2 be heated to required temperature, and then open pump of constant delivery type conveying reaction raw materials DMB-2 (material composition is in table 1,3,5,7), and writing time, inlet amount, temperature of reaction.

12), after the temperature-stable of tubular reactor 3, interval sampling detects, and record tubular reactor 3 temperature, the residence time, gas flow rate, observe the relation between the temperature of tubular reactor 3, gas flow rate, the transformation efficiency of the residence time and product, selectivity, observe the work-ing life of catalyzer, cycle.

Raw materials used and the device of 2,3-dimethyl-1-butylene prepared by table 1

Table 2 experimental result

1. catalyst treatment amount is 8.2g/g cat/h DMB-2.

2. production capacity is 1.23g/g cat/h DMB-1.

Can find out by the result that three different gas speed carry out isomerization reaction: when gas speed is at 9.1cm/s, the selectivity of DMB-1 is about 95%, when declining to some extent a little less than (6.7cm/s) selectivity during this gas speed, and transformation efficiency improves.

Raw materials used and the device of 2,3-dimethyl-1-butylene prepared by table 3

Table 4 experimental result

1. catalyst treatment amount is 10.6g/g cat/h DMB-2.

2. production capacity is 1.59g/g cat/h DMB-1.

Raw materials used and the device of 2,3-dimethyl-1-butylene prepared by table 5

Table 6 experimental result

1. catalyst treatment amount is 10.6g/g cat/h DMB-2.

2. production capacity is 1.59g/g cat/h DMB-1.

When gas speed is at 13.1-17.6cm/s, the transformation efficiency of DMB-2 is very low, and the growing amount of superpolymer does not reduce simultaneously, thus the selectivity of DMB-1 is reduced.

Be prepared with the DMB-2 raw material not through super-dry:

Raw materials used and the device of 2,3-dimethyl-1-butylene prepared by table 7

Table 8 experimental result

1. catalyst treatment amount is 10.3g/g cat/h DMB-2.

2. production capacity is 1.54g/g cat/h DMB-1.

Raw material is not through drying treatment, and the time of transformation efficiency more than 10% of DMB-2 only has 3.8h, and the work-ing life of catalyzer shortens greatly

Gas speed 10.3cm/s, temperature of reaction 110-130 DEG C, under raw material predrying (moisture is 115ppm) condition, time/transformation efficiency/selectivity relation as shown in Figure 2, under above reaction conditions: transformation efficiency is when 10-18%, and its selectivity can more than 95%.

Analytical procedure: HLGC

1. gas chromatograph: there is flame ionization ditector

2. chromatographic column: SE-30

3. gas-chromatography operational condition

Column temperature (Cheng Sheng temperature): starting temperature 36 DEG C, keeps 3min; 25 DEG C/min, rise to 260 DEG C, keep 3min.

Vaporizer temperature: 200 DEG C

Detector temperature: 200 DEG C

4. gas flow: (ml/min)

Carrier gas (N ₂): 30 (before post pressure 0.025Mpa)

Hydrogen: 30

Air: 300

5. sampling volume: 0.2 μ l

6. fractionation ratio: 1:30

Above-described embodiment, only for technical conceive of the present invention and feature are described, its object is to person skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences done according to spirit of the present invention change or modify, and all should be encompassed within protection scope of the present invention.

Claims (6)

1. gas-solid phase isocatalysis prepares 2, the method of 3-dimethyl-1-butylene, it is characterized in that: take tetramethyl-ethylene as raw material, Na-Y molecular sieve is adopted to be that catalyzer carries out gas phase isomerization reaction, finally prepare 2,3-dimethyl-1-butylene, wherein gas phase isomerization reaction temperature is at 110-130 DEG C, and the gasification temperature of raw material is at 120-140 DEG C.

2. prepare the method for 2,3-dimethyl-1-butylene according to gas-solid phase isocatalysis described in claim 1, it is characterized in that: control to enter the gas flow rate of reactor feedstocks at 7.5 ~ 12cm/s.

3. prepare the method for 2,3-dimethyl-1-butylene according to gas-solid phase isocatalysis described in claim 1, it is characterized in that: before reaction, the water content of raw material tetramethyl-ethylene is 60-100ppm.

4. prepare the method for 2,3-dimethyl-1-butylene according to gas-solid phase isocatalysis described in claim 1, it is characterized in that: gas flow rate is 10.3cm/s, the water content of tetramethyl-ethylene is 115ppm.

5. prepare 2 according to gas-solid phase isocatalysis described in claim 1, the method of 3-dimethyl-1-butylene, it is characterized in that, raw material tetramethyl-ethylene take propylene as raw material, be catalyst dimerization of propylene with two (tricyclohexyl phosphine) Nickel Chloride, through two to aggregate into, in cut, isomery, rectifying separation obtain tetramethyl-ethylene.

6. prepare the method for 2,3-dimethyl-1-butylene according to gas-solid phase isocatalysis described in claim 5, it is characterized in that, the preparation method of raw material tetramethyl-ethylene is:

1), prepare two (tricyclohexyl phosphine) Nickel Chloride toluene homogeneous phase solution and aluminum alkyls toluene homogeneous phase solution, wherein aluminum alkyls is sesquialter aluminium, is selected from diethyl aluminum chloride and/or ethylaluminum dichloride;

2), dipolymer reactor is shell and tube heat exchanger form, heat interchanging area 40m ²; Shell leads to cold, and sets temperature of reactor as-10 ~ 0 DEG C;

3), liquid propene flows through water cooler, and water cooler design temperature is-10 ~ 0 DEG C; Enter shell and tube reactor, add propylene 500L;

4), start reactor cycles pump, propylene feedstocks self-circulation is in reactor, and reactor cycles pump is canned-motor pump Q=15m ³/ hr;

5), the aluminum alkyls toluene homogeneous phase solution of 1 ~ 2L concentration to be two (tricyclohexyl phosphine) Nickel Chloride toluene homogeneous phase solution and 0.10 ~ 0.30L concentration of 0.05 ~ 1wt% be 10 ~ 20wt% presses volume pump to pump into shell-and-tube reactor in warp respectively;

6), at canned-motor pump Q=15m ³under the circulation promotion of/hr, there is dimerization reaction, control pressure 0.6 ~ 0.0MPa;

7), reaction residual voltage be under 0.0MPa, continue reaction 30min, off-response device recycle pump leads to the circulation valve of reactor, opens the arm valve leading to inactivation still simultaneously, carries out the process of water inactivation to reactant;

8), after inactivation dipolymer oil phase is after aqueous phase washing, and oil phase merges and obtains propylene dimer organic phase, through in cut, isomery, rectifying separation obtain 2,3-neohexene.