CN106040284B - A kind of support type NaHSO4Catalyst and its preparation method and application - Google Patents

A kind of support type NaHSO4Catalyst and its preparation method and application Download PDF

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Publication number
CN106040284B
CN106040284B CN201610378243.8A CN201610378243A CN106040284B CN 106040284 B CN106040284 B CN 106040284B CN 201610378243 A CN201610378243 A CN 201610378243A CN 106040284 B CN106040284 B CN 106040284B
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catalyst
nahso
support type
crude product
preparation
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CN106040284A (en
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丁建飞
严翠霞
马田林
邵荣
许伟
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Huzhou xinbeilian Network Technology Co.,Ltd.
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Yangcheng Institute of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself

Abstract

A kind of support type NaHSO4The preparation method of catalyst, belongs to field of catalytic chemistry, comprising the following steps: carrier material is impregnated in NaHSO4In aqueous solution, slurry is stirred to get；Slurry is placed in N2In environment, heating, pressurization makes N2Reach super critical condition and continue 2~12h, then through cooling down, pressure release obtains catalyst crude product；Catalyst crude product is dry, obtain support type NaHSO4Catalyst.Furthermore the invention further relates to a kind of support type NaHSO prepared by the above method4Catalyst and its in castor oil dehydration prepare the application in dehydrated castor oil.This method time-saving and efficiency, it is easy to operate.The support type NaHSO prepared4Catalyst dispersity can be good, and catalytic activity is high, is easily recycled.With the castor oil dehydration of the catalyst, the iodine number of reaction product is improved, the hydroxyl value of product is reduced, effectively slows down the loss of catalyst activity component.

Description

A kind of support type NaHSO4Catalyst and its preparation method and application
Technical field
The present invention relates to a kind of field of catalytic chemistry, and in particular to a kind of support type NaHSO4Catalyst and its preparation side Method and application.
Background technique
Catalyst can play the role of accelerating reaction in chemical reaction, be widely used in chemical industry, petrochemical industry, biochemistry, ring The fields such as guarantor.With the development of science and technology, traditional catalyst often exist the low, poor selectivity of activity, difficult separation and recycling, The disadvantages of polluting environment, is increasingly valued by people the transformation of catalyst, under the premise of such, loaded catalyst Just it comes into being.Loaded catalyst is that traditional catalyst is evenly dispersed and is supported on specific carrier material, is increased The contact area of catalyst and reaction substrate can effectively improve reactivity and selectivity.Meanwhile loaded catalyst is stablized Property it is good, be also very to facilitate in terms of recycling with recycling.
NaHSO4Aqueous solution be in highly acid, often as a kind of acidic catalyst come using, particularly with catalyzing and condensing, Dehydration is quite effective, has many advantages, such as that cheap and easy to get, reaction condition is mild.For example, in castor oil dehydration, NaHSO4Catalyst is compared with other catalyst, has many advantages, such as that few by-product, high conversion rate, the quality of product are high, but There is separating-purifying difficulty after reaction is big, it is unfavorable for catalyst reuse, the problems such as catalyst easy in inactivation.
Summary of the invention
The first object of the present invention is to provide a kind of support type NaHSO4The manufacture craft of catalyst, this method operation letter It is single, have many advantages, such as to reduce catalyst activity component turnover rate.
The second object of the present invention is to provide a kind of support type NaHSO4Catalyst, support type NaHSO4Catalyst tool Have that dispersion performance is good, catalytic activity is high, and convenient for recycling with recycling the advantages that.
The third object of the present invention is to provide a kind of support type NaHSO4Catalyst answering in castor oil dehydration With using the castor oil dehydration of the catalyst, capable of effectively improving reactivity and conversion ratio, and can react It very easily separates and reuses afterwards.
The present invention solves its technical problem and adopts the following technical solutions to realize.
The present invention proposes a kind of support type NaHSO4The preparation method of catalyst, comprising the following steps:
Carrier material is impregnated in NaHSO4In aqueous solution, it is uniformly mixed to obtain slurry；Above-mentioned slurry is set In N2In environment, heating, pressurization make N2Reach super critical condition and continue 2~12h, then through cooling down, it is thick to obtain catalyst for pressure release Product, above-mentioned super critical condition are 20~80 DEG C of temperature, 4~12MPa of pressure；Above-mentioned catalyst crude product is stood, it is dry, it is born Load type NaHSO4Catalyst.
The present invention proposes a kind of support type NaHSO4Catalyst uses above-mentioned preparation method to be made.
The present invention proposes a kind of above-mentioned support type NaHSO4Catalyst prepares answering in dehydrated castor oil in castor oil dehydration With.
A kind of support type NaHSO of the embodiment of the present invention4The beneficial effect of catalyst and its preparation method and application is: super Critical technology has been developed in recent years emerging technology, and at supercritical conditions, the viscosity of fluid and diffusion coefficient are close to gas Body, and density and solvability are close to liquid.Supercritical fluid has the advantages that dissolubility is strong, diffusion is good.The present invention The overcritical N provided2Under prepare support type NaHSO4The method of catalyst can allow catalyst to disperse on a support material more Uniformly, load factor is high.Method time-saving and efficiency itself, it is easy to operate.The support type NaHSO prepared with this method4Catalyst point It is good to dissipate performance, catalytic activity is high, and is easily recycled and reuses.The catalyst is applied in castor oil dehydration, is had The iodine number for improving reaction product of effect, reduces the hydroxyl value of product, and separation and reuse all ten after reaction It is convenient to divide.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase Product.
Below to a kind of support type NaHSO of the embodiment of the present invention4Catalyst and its preparation method and application carries out specific Explanation.
The embodiment of the present invention proposes a kind of support type NaHSO4The preparation method of catalyst, comprising the following steps:
Step A: carrier material is impregnated in NaHSO4In aqueous solution, it is uniformly mixed to obtain slurry.
Specifically, at least one of carrier material MCM-41, MCM-48, MCM-50 and FSM-16.MCM-41, MCM-48, MCM-50 and FSM-16 are molecular sieve, and can directly buy and obtain from market.
NaHSO4Mass ratio with the carrier material is 0.173~0.547:1.NaHSO4With the matter of the carrier material Amount is than being 0.429~0.538:1.NaHSO in catalyst4Amount it is very little, in Catalysis experiments, be difficult to observe its catalysis effect Fruit, and NaHSO4Amount too much then can be more than carrier material load limit, cause the blocking in duct on carrier material.
Step B: above-mentioned slurry is placed in N2In environment, heating, pressurization make N2Reach super critical condition and continue 2~ 12h, then through cooling down, pressure release obtains catalyst crude product.Super critical condition is 20~80 DEG C of temperature, 4~12MPa of pressure.Preferably Ground, super critical condition are 40~80 DEG C of temperature, 8~10MPa of pressure.
Step C: dry above-mentioned catalyst crude product obtains support type NaHSO4Catalyst.
Before catalyst crude product is dried, preferably, can first be stood to catalyst crude product.Static conditions are 2~12h is stood in 20~30 DEG C.Standing process is conducive to NaHSO4Into the duct on carrier material, time of repose is too short to be made It is insufficient at loading.
In a preferred embodiment of the present invention, the drying condition of catalyst crude product is dry 3~12h at 80~120 DEG C.Temperature The too low or time is too short, can all make the residual moisture in catalyst, not only will cause catalyst actual mass inaccuracy, can also shadow Ring catalytic effect.
The embodiment of the present invention is it is also proposed that a kind of support type NaHSO4Catalyst uses above-mentioned preparation method to be made.Compared with Good, obtained support type NaHSO4In catalyst, NaHSO4Load capacity is 10~70wt%.
The embodiment of the present invention also proposes a kind of support type NaHSO4Catalyst is prepared in dehydrated castor oil in castor oil dehydration Application.
When castor oil dehydration prepares dehydrated castor oil, using fixed bed reactors, support type NaHSO is added4Catalyst, Using pure castor oil as raw material, the dehydrated castor oil that preparation reaction obtains is carried out.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
The present embodiment provides one kind in overcritical N2The NaHSO prepared in environment4/ MCM-41 catalyst, preparation step It is as follows:
Step A: by 0.177g NaHSO in reaction kettle4It is dissolved in the deionized water of 2.4ml, is uniformly mixed to obtain NaHSO4Aqueous solution, by 1g MCM-41 carrier impregnation in above-mentioned NaHSO4In aqueous solution, it is uniformly mixed to obtain slurry；
Step B: with high pressure syringe pump by N2Gas is filled with reaction kettle, and pressure in kettle is made to reach 6MPa, then uses program Reactor temperature is raised to 60 DEG C by heating, to reach super critical condition, then maintains super critical condition 6h, first supercritical processing is complete Bi Hou, cooling, pressure release unload kettle, obtain catalyst crude product；
Step C: catalyst crude product being placed in beaker and stands 8h at 20 °C, is then put into catalyst crude product 4h is dried in baking oven and under the conditions of 90 DEG C, obtains NaHSO4/ MCM-41 catalyst.
Embodiment 2
The present embodiment provides one kind in overcritical N2The NaHSO prepared in environment4/ MCM-41 catalyst, preparation step It is as follows:
Step A: by 0.25g NaHSO in reaction kettle4It is dissolved in the deionized water of 2.4ml, is uniformly mixed to obtain NaHSO4Aqueous solution, by 1g MCM-41 carrier impregnation in above-mentioned NaHSO4In aqueous solution, it is uniformly mixed to obtain slurry；
Step B: with high pressure syringe pump by N2Gas is filled with reaction kettle, and pressure in kettle is made to reach 12MPa, then uses journey Reactor temperature is raised to 70 DEG C by sequence heating, to reach super critical condition, then maintains super critical condition 2h, first supercritical processing After, cooling, pressure release unloads kettle, obtains catalyst crude product；
Step C: catalyst crude product being placed in beaker and stands 4h at 20 °C, is then put into catalyst crude product 8h is dried in baking oven and under the conditions of 110 DEG C, obtains NaHSO4/ MCM-41 catalyst.
Embodiment 3
The present embodiment provides one kind in overcritical N2The NaHSO prepared in environment4/ MCM-41 catalyst, preparation step It is as follows:
Step A: by 0.333g NaHSO in reaction kettle4It is dissolved in the deionized water of 2.4ml, is uniformly mixed to obtain NaHSO4Aqueous solution, by 1g MCM-41 carrier impregnation in above-mentioned NaHSO4In aqueous solution, it is uniformly mixed to obtain slurry；
Step B: with high pressure syringe pump by N2Gas is filled with reaction kettle, and pressure in kettle is made to reach 12MPa, then uses journey Reactor temperature is raised to 50 DEG C by sequence heating, to reach super critical condition, then maintains super critical condition 12h, overcritical place After reason, cooling, pressure release unloads kettle, obtains catalyst crude product；
Step C: catalyst crude product is placed in beaker and stands 12h under the conditions of 25 DEG C, then puts catalyst crude product Enter in baking oven and dry 10h under the conditions of 100 DEG C, obtains NaHSO4/ MCM-41 catalyst.
Embodiment 4
The present embodiment provides one kind in overcritical N2The NaHSO prepared in environment4/ MCM-41 catalyst, preparation step It is as follows:
Step A: by 0.429g NaHSO in reaction kettle4It is dissolved in the deionized water of 2.4ml, is uniformly mixed to obtain NaHSO4Aqueous solution, by 1g MCM-41 carrier impregnation in above-mentioned NaHSO4In aqueous solution, it is uniformly mixed to obtain slurry；
Step B: with high pressure syringe pump by N2Gas is filled with reaction kettle, and pressure in kettle is made to reach 10MPa, then uses journey Reactor temperature is raised to 80 DEG C by sequence heating, to reach super critical condition, then maintains super critical condition 10h, overcritical place After reason, cooling, pressure release unloads kettle, obtains catalyst crude product；
Step C: catalyst crude product is placed in beaker and stands 6h under the conditions of 30 DEG C, is then put into catalyst crude product 10h is dried in baking oven and under the conditions of 120 DEG C, obtains NaHSO4/ MCM-41 catalyst.
Embodiment 5
The present embodiment provides one kind in overcritical N2The NaHSO prepared in environment4/ MCM-41 catalyst, preparation step It is as follows:
Step A: by 0.538g NaHSO in reaction kettle4It is dissolved in the deionized water of 2.4ml, is uniformly mixed to obtain NaHSO4Aqueous solution, by 1g MCM-41 carrier impregnation in above-mentioned NaHSO4In aqueous solution, it is uniformly mixed to obtain slurry；
Step B: with high pressure syringe pump by N2Gas is filled with reaction kettle, and pressure in kettle is made to reach 8MPa, then uses program Reactor temperature is raised to 40 DEG C by heating, to reach super critical condition, then maintains super critical condition 8h, first supercritical processing is complete Bi Hou, cooling, pressure release unload kettle, obtain catalyst crude product；
Step C: catalyst crude product is placed in beaker and stands 10h under the conditions of 25 DEG C, then puts catalyst crude product Enter in baking oven and dry 6h under the conditions of 80 DEG C, obtains NaHSO4/ MCM-41 catalyst.
Embodiment 6
The present embodiment provides one kind in overcritical N2The NaHSO prepared in environment4/ MCM-48 catalyst, preparation step It is as follows:
Step A: by 0.173g NaHSO in reaction kettle4It is dissolved in the deionized water of 2.4ml, is uniformly mixed to obtain NaHSO4Aqueous solution, by 1g MCM-48 carrier impregnation in above-mentioned NaHSO4In aqueous solution, it is uniformly mixed to obtain slurry；
Step B: with high pressure syringe pump by N2Gas is filled with reaction kettle, and pressure in kettle is made to reach 4MPa, then uses program Reactor temperature is raised to 60 DEG C by heating, to reach super critical condition, then maintains super critical condition 8h, first supercritical processing is complete Bi Hou, cooling, pressure release unload kettle, obtain catalyst crude product；
Step C: catalyst crude product is placed in beaker and stands 2h under the conditions of 30 DEG C, is then put into catalyst crude product 8h is dried in baking oven and under the conditions of 100 DEG C, obtains NaHSO4/ MCM-48 catalyst.
Embodiment 7
The present embodiment provides one kind in overcritical N2The NaHSO prepared in environment4/ MCM-50 catalyst, preparation step It is as follows:
Step A: by 0.452g NaHSO in reaction kettle4It is dissolved in the deionized water of 2.4ml, is uniformly mixed to obtain NaHSO4Aqueous solution, by 1g MCM-50 carrier impregnation in above-mentioned NaHSO4In aqueous solution, it is uniformly mixed to obtain slurry；
Step B: with high pressure syringe pump by N2Gas is filled with reaction kettle, and pressure in kettle is made to reach 8MPa, then uses program Reactor temperature is raised to 60 DEG C by heating, to reach super critical condition, then maintains super critical condition 6h, first supercritical processing is complete Bi Hou, cooling, pressure release unload kettle, obtain catalyst crude product；
Step C: catalyst crude product is placed in beaker and stands 4h under the conditions of 25 DEG C, is then put into catalyst crude product 4h is dried in baking oven and under the conditions of 100 DEG C, obtains NaHSO4/ MCM-50 catalyst.
Embodiment 8
The present embodiment provides one kind in overcritical N2The NaHSO prepared in environment4/ FSM-16 catalyst, preparation step It is as follows:
Step A: by 0.547g NaHSO in reaction kettle4It is dissolved in the deionized water of 2.4ml, is uniformly mixed to obtain NaHSO4Aqueous solution, by 1g FSM-16 carrier impregnation in above-mentioned NaHSO4In aqueous solution, it is uniformly mixed to obtain slurry；
Step B: with high pressure syringe pump by N2Gas is filled with reaction kettle, and pressure in kettle is made to reach 10MPa, then uses journey Reactor temperature is raised to 20 DEG C by sequence heating, to reach super critical condition, then maintains super critical condition 4h, first supercritical processing After, cooling, pressure release unloads kettle, obtains catalyst crude product；
Step C: catalyst crude product is placed in beaker and stands 4h under the conditions of 25 DEG C, is then put into catalyst crude product 3h is dried in baking oven and under the conditions of 100 DEG C, obtains NaHSO4/ FSM-16 catalyst.
Comparative example 1
This comparative example provides a kind of NaHSO prepared using conventional impregnation4/ MCM-41 catalyst, preparation step is such as Under:
Step A: by 0.177g NaHSO in beaker4It is dissolved in the deionized water of 2.4ml, is uniformly mixed to obtain NaHSO4Aqueous solution, then by 1g MCM-41 carrier impregnation in above-mentioned solution NaHSO4In aqueous solution, it is ultrasonically treated 2h, is catalyzed Agent crude product；
Step B: standing 8h for catalyst crude product at 20 DEG C, then catalyst crude product is put into baking oven and in 90 DEG C of items Dry 4h, obtains NaHSO under part4/ MCM-41 catalyst.
Comparative example 2
This comparative example provides a kind of NaHSO prepared using conventional impregnation4/ MCM-41 catalyst, preparation step is such as Under:
Step A: by 0.25g NaHSO in beaker4It is dissolved in the deionized water of 2.4ml, is uniformly mixed to obtain NaHSO4Aqueous solution, then by 1g MCM-41 carrier impregnation in above-mentioned solution NaHSO4In aqueous solution, it is ultrasonically treated 2h, is catalyzed Agent crude product；
Step B: standing 4h for catalyst crude product at 20 DEG C, then catalyst crude product is put into baking oven and at 110 DEG C Under the conditions of dry 8h, obtain NaHSO4/ MCM-41 catalyst.
Comparative example 3
This comparative example provides a kind of NaHSO prepared using conventional impregnation4/ MCM-41 catalyst, preparation step is such as Under:
Step A: by 0.333g NaHSO in beaker4It is dissolved in the deionized water of 2.4ml, is uniformly mixed to obtain NaHSO4Aqueous solution, then by 1g MCM-41 carrier impregnation in above-mentioned solution NaHSO4In aqueous solution, it is ultrasonically treated 2h, is catalyzed Agent crude product；
Step B: standing 12h for catalyst crude product at 25 DEG C, then catalyst crude product is put into baking oven and at 100 DEG C Under the conditions of dry 11h, obtain NaHSO4/ MCM-41 catalyst.
Comparative example 4
This comparative example provides a kind of NaHSO prepared using conventional impregnation4/ MCM-41 catalyst, preparation step is such as Under:
Step A: by 0.429g NaHSO in beaker4It is dissolved in the deionized water of 2.4ml, is uniformly mixed to obtain NaHSO4Aqueous solution, then by 1g MCM-41 carrier impregnation in above-mentioned solution NaHSO4In aqueous solution, it is ultrasonically treated 2h, is catalyzed Agent crude product；
Step B: standing 6h for catalyst crude product at 30 DEG C, then catalyst crude product is put into baking oven and at 120 DEG C Under the conditions of dry 10h, obtain NaHSO4/ MCM-41 catalyst.
Comparative example 5
This comparative example provides a kind of NaHSO prepared using conventional impregnation4/ MCM-41 catalyst, preparation step is such as Under:
Step A: by 0.538g NaHSO in beaker4It is dissolved in the deionized water of 2.4ml, is uniformly mixed to obtain NaHSO4Aqueous solution, then by 1g MCM-41 carrier impregnation in above-mentioned solution NaHSO4In aqueous solution, it is ultrasonically treated 2h, is catalyzed Agent crude product；
Step B: standing 10h for catalyst crude product at 25 DEG C, then catalyst crude product is put into baking oven and at 80 DEG C Under the conditions of dry 6h, obtain NaHSO4/ MCM-41 catalyst.
Application examples
Using fixed bed reactors, 0.5g support type NaHSO is added4Catalyst is being reacted using pure castor oil as raw material 230 DEG C of temperature, mass space velocity 0.7h-1Under tested, be individually for portion according to the dehydrated castor oil that each hour obtains, with To the dehydrated castor oil of more parts of different iodine numbers and hydroxyl value.
Experimental example
Support type NaHSO made from method using embodiment 1-8 and comparative example 1-54Catalyst is dehydrated as castor oil Catalyst in reaction, and test its catalytic effect in castor oil dehydration.Experiment uses fixed bed reactors, with pure Castor oil is as raw material, support type NaHSO4Catalyst amount 0.5g, reaction temperature are 230 DEG C, mass space velocity 0.7h-1Under It carries out, and the indices of obtained dehydrated castor oil is tested.
1, the iodine number of dehydrated castor oil is tested according to GB/T 5532-2008 " measurement of animal and plant fat iodine number ", is surveyed Test result is shown in Table 1；
2, the hydroxyl value of dehydrated castor oil is according to SN/T 0801.20-1999 " inlet and outlet animal and plant fat hydroxyl value detection method " It is tested, test result is shown in Table 1；
3, support type NaHSO is measured using ICP method4Sulfur content A before catalyst reaction.After reaction, load is taken out Type NaHSO4Catalyst measures support type NaHSO using ICP method after drying4The sulfur content B of catalyst.Then it calculates according to the following formula Support type NaHSO out4The turnover rate of catalyst, turnover rate=(sulfur content A- sulfur content B)/sulfur content A*100% calculate knot Fruit is shown in Table 1.
1. dehydrated castor oil indices testing result of table
As it can be seen from table 1 support type NaHSO made from the method for 1-8 of the embodiment of the present invention4Catalyst and pass through tradition Support type NaHSO made from infusion process4Catalyst (comparative example 1-5) is compared, and the effect for being catalyzed reaction is more excellent.Specifically, exist In the reaction of castor oil dehydration, initial 1h is reacted, the one kind provided using 1-8 of the embodiment of the present invention is in overcritical N2In environment The support type NaHSO of preparation4The dehydrated castor oil that catalyst obtains and the support type NaHSO using conventional impregnation preparation4Catalysis The iodine number and hydroxyl value for the dehydrated castor oil that agent (comparative example 1-5) obtains are suitable, and when reaction proceeds to 10h, using the present invention The support type NaHSO that embodiment provides4The dehydrated castor oil that catalyst obtains has higher iodine number and lower hydroxyl value.Pass through To support type NaHSO4Catalyst turnover rate of active component before and after reaction is measured, it has been found that the embodiment of the present invention The support type NaHSO of offer4Rear loss of active component rate is low before the reaction for catalyst, so that the catalyst can be for a long time Holding to the catalytic activity of castor oil dehydration.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Reality of the invention The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of selected implementation of the invention Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts Every other embodiment, shall fall within the protection scope of the present invention.

Claims (8)

1. a kind of support type NaHSO4The preparation method of catalyst, which is characterized in that itself the following steps are included:
Carrier material is impregnated in NaHSO4In aqueous solution, it is uniformly mixing to obtain slurry；The slurry is placed in N2Environment In, heating, pressurization make N2Reach super critical condition and continue 2~12h, then obtains catalyst crude product through cooling, pressure release, it is described super Critical condition is 20~80 DEG C of temperature, 4~12MPa of pressure；The catalyst crude product is dry, obtain the support type NaHSO4 Catalyst；The carrier material is at least one of MCM-41, MCM-48, MCM-50 and FSM-16.
2. preparation method according to claim 1, which is characterized in that the super critical condition is 40~80 DEG C of temperature, pressure Strong 8~10MPa.
3. preparation method according to claim 1, which is characterized in that the NaHSO4With the mass ratio of the carrier material For 0.173~0.547:1.
4. preparation method according to claim 1, which is characterized in that the NaHSO4With the mass ratio of the carrier material For 0.429~0.538:1.
5. the preparation method according to claim 4, which is characterized in that the catalyst crude product further includes standing before it is dried Step, the condition for standing step are that 2~12h is stood at 20~30 DEG C.
6. preparation method according to claim 5, which is characterized in that the drying condition of the catalyst crude product be 80~ Dry 3~12h at 120 DEG C.
7. a kind of support type NaHSO4Catalyst, which is characterized in that use preparation method as claimed in any one of claims 1 to 6 It is made.
8. a kind of support type NaHSO as claimed in claim 74Catalyst prepares answering in dehydrated castor oil in castor oil dehydration With.
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