CN106040284A - Supported NaHSO4 catalyst and preparation method and application thereof - Google Patents

Supported NaHSO4 catalyst and preparation method and application thereof Download PDF

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Publication number
CN106040284A
CN106040284A CN201610378243.8A CN201610378243A CN106040284A CN 106040284 A CN106040284 A CN 106040284A CN 201610378243 A CN201610378243 A CN 201610378243A CN 106040284 A CN106040284 A CN 106040284A
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catalyst
nahso
preparation
crude product
support type
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CN106040284B (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

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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Dispersion Chemistry (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides a preparation method of a supported NaHSO4 catalyst and belongs to the field of catalytic chemistry. The preparation method includes the following steps that a carrier material is soaked in a NaHSO4 water solution, and pulp is obtained after stirring is completed; the pulp is put in an N2 environment, the temperature is raised, the pressure is increased, N2 reaches the supercritical condition and lasts for 2-12 h, and a crude catalyst is obtained after cooling and pressure relief; the crude catalyst is dried, and the supported NaHSO4 catalyst is obtained. In addition, the invention relates to the supported NaHSO4 catalyst prepared through the method and application of the supported NaHSO4 catalyst to preparation of dehydrated castor oil through dehydration of castor oil. The method saves time, and is efficient and easy and convenient to operate. The prepared supported NaHSO4 catalyst is good in dispersibility, the catalytic activity is high, and recovery is easy. Through the castor oil dehydration reaction catalyzed by the catalyst, the iodine value of reaction products is increased, the hydroxyl value of the products is reduced, and losses of active components of the catalyst are effectively retarded.

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 particularly to a kind of support type NaHSO4Catalyst and preparation side thereof Method and application.
Background technology
Catalyst can play the effect accelerating reaction in chemical reaction, is widely used in chemical industry, petrochemical industry, biochemistry, ring The fields such as guarantor.Along with the development of science and technology, traditional catalyst often exist activity low, poor selectivity, difficult separation and recycling, Polluting the shortcomings such as environment, the transformation to catalyst is increasingly subject to people's attention, on the premise of so, and loaded catalyst Just arise at the historic moment.Loaded catalyst is by dispersed for traditional catalyst and be supported on specific carrier material, adds Catalyst and the contact area of reaction substrate, can effectively improve reactivity and selectivity.Meanwhile, loaded catalyst is stable Property good, reclaim with recycling in terms of be also convenience very.
NaHSO4Aqueous solution be highly acid, use often as a kind of acidic catalyst, particularly with catalyzing and condensing, Dehydration is quite effective, and it has the advantages such as cheap and easy to get, reaction condition is gentle.Such as, in Oleum Ricini dehydration, NaHSO4Catalyst is compared with other catalyst, has that by-product is few, conversion ratio is high, the quality advantages of higher of product, but also The problems such as after there is reaction, separating-purifying difficulty is big, is unfavorable for that catalyst is reused, catalyst easy in inactivation.
Summary of the invention
The first object of the present invention is to provide a kind of support type NaHSO4The processing technology of catalyst, the method operation letter Single, there is the advantages such as reduction catalyst activity component turnover rate.
The second object of the present invention is to provide a kind of support type NaHSO4Catalyst, this support type NaHSO4Catalyst has Have that dispersive property is good, catalysis activity is high, and be easy to reclaim and the advantage such as recycling.
The third object of the present invention is to provide a kind of support type NaHSO4Catalyst answering in Oleum Ricini dehydration With, use the Oleum Ricini dehydration of this catalyst, can effectively improve reactivity and conversion ratio, and can react After separate very easily and reuse.
The present invention solves it and technical problem is that and realize by the following technical solutions.
The present invention proposes a kind of support type NaHSO4The preparation method of catalyst, comprises the following steps:
Carrier material be impregnated in NaHSO4In aqueous solution, it is uniformly mixed and obtains slurry；Above-mentioned slurry is put In N2In environment, heat up, supercharging makes N2Reach super critical condition persistently 2～12h, then through cooling, pressure release, obtain catalyst thick Product, above-mentioned super critical condition is temperature 20～80 DEG C, pressure 4～12MPa；Above-mentioned catalyst crude product is stood, is dried, is born Load type NaHSO4Catalyst.
The present invention proposes a kind of support type NaHSO4Catalyst, it uses above-mentioned preparation method to prepare.
The present invention proposes a kind of above-mentioned support type NaHSO4Catalyst prepares answering in dehydrated castor oil in Oleum Ricini dehydration With.
A kind of support type NaHSO of the embodiment of the present invention4Catalyst and its preparation method and application provides the benefit that: super Critical technology is the emerging technology grown up in recent years, 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 advantage that dissolubility is strong, diffusion is good.The present invention The supercritical N provided2Under prepare support type NaHSO4The method of catalyst, it is possible to allow catalyst disperse on a support material more Uniformly, load factor is high.The time-saving and efficiency of method own, easy and simple to handle.The support type NaHSO prepared by the method4Catalyst divides Dissipating performance good, catalysis activity is high, and is easily recycled and reuses.This catalyst is applied in Oleum Ricini dehydration, has The iodine number that improve product of effect, reduces the hydroxyl value of product, and separation after reaction and reuse all ten It is convenient to divide.
Detailed description of the invention
For making the purpose of the embodiment of the present invention, technical scheme and advantage clearer, below will be in the embodiment of the present invention Technical scheme be clearly and completely described.In embodiment, unreceipted actual conditions person, builds according to normal condition or manufacturer The condition of view is carried out.Agents useful for same or instrument unreceipted production firm person, being can be by the commercially available conventional product bought and obtain Product.
A kind of support type NaHSO to the embodiment of the present invention below4Catalyst and its preparation method and application is carried out specifically Explanation.
The embodiment of the present invention proposes a kind of support type NaHSO4The preparation method of catalyst, comprises the following steps:
Step A: carrier material be impregnated in NaHSO4In aqueous solution, it is uniformly mixed and obtains slurry.
Specifically, at least one during carrier material is MCM-41, MCM-48, MCM-50 and FSM-16.MCM-41、MCM- 48, MCM-50 and FSM-16 is molecular sieve, and all directly can buy from market and obtain.
NaHSO4It is 0.173～0.547:1 with the mass ratio of described carrier material.NaHSO4Matter with described carrier material Amount ratio is 0.429～0.538:1.NaHSO in catalyst4Amount very little, in Catalysis experiments, be difficult to observe its catalysis effect Really, NaHSO4Amount the most then can exceed the load limit of carrier material, cause the blocking in duct on carrier material.
Step B: above-mentioned slurry is placed in N2In environment, heat up, supercharging makes N2Reach super critical condition and persistently 2～ 12h, then through cooling, pressure release, obtain catalyst crude product.Super critical condition is temperature 20～80 DEG C, pressure 4～12MPa.Preferably Ground, super critical condition is temperature 40～80 DEG C, pressure 8～10MPa.
Step C: be dried above-mentioned catalyst crude product, obtain support type NaHSO4Catalyst.
Before catalyst crude product is dried, it is preferred that can first catalyst crude product be stood.Static conditions is 20～30 DEG C stand 2～12h.Standing process is beneficial to NaHSO4Entering the duct on carrier material, the too short meeting of time of repose is made Become load insufficient.
In present pre-ferred embodiments, the drying condition of catalyst crude product is to be dried 3～12h at 80～120 DEG C.Temperature Too low or the time is too short, all can make the moisture entrapment in catalyst, catalyst actual mass not only can be caused inaccurate, also can shadow Ring catalytic effect.
The embodiment of the present invention is it is also proposed that a kind of support type NaHSO4Catalyst, it uses above-mentioned preparation method to prepare.Relatively 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 Oleum Ricini dehydration Application.
When dehydrated castor oil is prepared in Oleum Ricini dehydration, use fixed bed reactors, add support type NaHSO4Catalyst, Using pure Oleum Ricini as raw material, it is prepared the dehydrated castor oil that reaction obtains.
Below in conjunction with embodiment, inventive feature and performance are described in further detail.
Embodiment 1
The present embodiment provides a kind of at supercritical N2The NaHSO of preparation in environment4/ MCM-41 catalyst, its preparation process is such as Under:
Step A: by 0.177g NaHSO in reactor4It is dissolved in the deionized water of 2.4ml, is uniformly mixed and obtains NaHSO4Aqueous solution, by 1g MCM-41 carrier impregnation in above-mentioned NaHSO4In aqueous solution, it is uniformly mixed and obtains slurry；
Step B: with high pressure syringe pump by N2Gas is filled with reactor, and in making still, pressure reaches 6MPa, then uses program Heating up and reactor temperature is raised to 60 DEG C, to reach super critical condition, then maintain super critical condition 6h, first supercritical processing is complete Bi Hou, cooling, pressure release, unload still, obtain catalyst crude product；
Step C: catalyst crude product is positioned in beaker standing 8h under the conditions of 20 DEG C, then catalyst crude product is put into It is dried 4h in baking oven and under the conditions of 90 DEG C, obtains NaHSO4/ MCM-41 catalyst.
Embodiment 2
The present embodiment provides a kind of at supercritical N2The NaHSO of preparation in environment4/ MCM-41 catalyst, its preparation process is such as Under:
Step A: by 0.25g NaHSO in reactor4It is dissolved in the deionized water of 2.4ml, is uniformly mixed and obtains NaHSO4Aqueous solution, by 1g MCM-41 carrier impregnation in above-mentioned NaHSO4In aqueous solution, it is uniformly mixed and obtains slurry；
Step B: with high pressure syringe pump by N2Gas is filled with reactor, and in making still, pressure reaches 12MPa, then uses program Heating up and reactor temperature is raised to 70 DEG C, to reach super critical condition, then maintain super critical condition 2h, first supercritical processing is complete Bi Hou, cooling, pressure release, unload still, obtain catalyst crude product；
Step C: catalyst crude product is positioned in beaker standing 4h under the conditions of 20 DEG C, then catalyst crude product is put into It is dried 8h in baking oven and under the conditions of 110 DEG C, obtains NaHSO4/ MCM-41 catalyst.
Embodiment 3
The present embodiment provides a kind of at supercritical N2The NaHSO of preparation in environment4/ MCM-41 catalyst, its preparation process is such as Under:
Step A: by 0.333g NaHSO in reactor4It is dissolved in the deionized water of 2.4ml, is uniformly mixed and obtains NaHSO4Aqueous solution, by 1g MCM-41 carrier impregnation in above-mentioned NaHSO4In aqueous solution, it is uniformly mixed and obtains slurry；
Step B: with high pressure syringe pump by N2Gas is filled with reactor, and in making still, pressure reaches 12MPa, then uses program Heat up and reactor temperature is raised to 50 DEG C, to reach super critical condition, then maintain super critical condition 12h, first supercritical processing After, cooling, pressure release, unload still, obtain catalyst crude product；
Step C: catalyst crude product is positioned in beaker standing 12h under the conditions of 25 DEG C, then catalyst crude product is put Enter in baking oven and under the conditions of 100 DEG C, be dried 10h, obtaining NaHSO4/ MCM-41 catalyst.
Embodiment 4
The present embodiment provides a kind of at supercritical N2The NaHSO of preparation in environment4/ MCM-41 catalyst, its preparation process is such as Under:
Step A: by 0.429g NaHSO in reactor4It is dissolved in the deionized water of 2.4ml, is uniformly mixed and obtains NaHSO4Aqueous solution, by 1g MCM-41 carrier impregnation in above-mentioned NaHSO4In aqueous solution, it is uniformly mixed and obtains slurry；
Step B: with high pressure syringe pump by N2Gas is filled with reactor, and in making still, pressure reaches 10MPa, then uses program Heat up and reactor temperature is raised to 80 DEG C, to reach super critical condition, then maintain super critical condition 10h, first supercritical processing After, cooling, pressure release, unload still, obtain catalyst crude product；
Step C: catalyst crude product is positioned in beaker standing 6h under the conditions of 30 DEG C, then catalyst crude product is put into It is dried 10h in baking oven and under the conditions of 120 DEG C, obtains NaHSO4/ MCM-41 catalyst.
Embodiment 5
The present embodiment provides a kind of at supercritical N2The NaHSO of preparation in environment4/ MCM-41 catalyst, its preparation process is such as Under:
Step A: by 0.538g NaHSO in reactor4It is dissolved in the deionized water of 2.4ml, is uniformly mixed and obtains NaHSO4Aqueous solution, by 1g MCM-41 carrier impregnation in above-mentioned NaHSO4In aqueous solution, it is uniformly mixed and obtains slurry；
Step B: with high pressure syringe pump by N2Gas is filled with reactor, and in making still, pressure reaches 8MPa, then uses program Heating up and reactor temperature is raised to 40 DEG C, to reach super critical condition, then maintain super critical condition 8h, first supercritical processing is complete Bi Hou, cooling, pressure release, unload still, obtain catalyst crude product；
Step C: catalyst crude product is positioned in beaker standing 10h under the conditions of 25 DEG C, then catalyst crude product is put Enter in baking oven and under the conditions of 80 DEG C, be dried 6h, obtaining NaHSO4/ MCM-41 catalyst.
Embodiment 6
The present embodiment provides a kind of at supercritical N2The NaHSO of preparation in environment4/ MCM-48 catalyst, its preparation process is such as Under:
Step A: by 0.173g NaHSO in reactor4It is dissolved in the deionized water of 2.4ml, is uniformly mixed and obtains NaHSO4Aqueous solution, by 1g MCM-48 carrier impregnation in above-mentioned NaHSO4In aqueous solution, it is uniformly mixed and obtains slurry；
Step B: with high pressure syringe pump by N2Gas is filled with reactor, and in making still, pressure reaches 4MPa, then uses program Heating up and reactor temperature is raised to 60 DEG C, to reach super critical condition, then maintain super critical condition 8h, first supercritical processing is complete Bi Hou, cooling, pressure release, unload still, obtain catalyst crude product；
Step C: catalyst crude product is positioned in beaker standing 2h under the conditions of 30 DEG C, then catalyst crude product is put into It is dried 8h in baking oven and under the conditions of 100 DEG C, obtains NaHSO4/ MCM-48 catalyst.
Embodiment 7
The present embodiment provides a kind of at supercritical N2The NaHSO of preparation in environment4/ MCM-50 catalyst, its preparation process is such as Under:
Step A: by 0.452g NaHSO in reactor4It is dissolved in the deionized water of 2.4ml, is uniformly mixed and obtains NaHSO4Aqueous solution, by 1g MCM-50 carrier impregnation in above-mentioned NaHSO4In aqueous solution, it is uniformly mixed and obtains slurry；
Step B: with high pressure syringe pump by N2Gas is filled with reactor, and in making still, pressure reaches 8MPa, then uses program Heating up and reactor temperature is raised to 60 DEG C, to reach super critical condition, then maintain super critical condition 6h, first supercritical processing is complete Bi Hou, cooling, pressure release, unload still, obtain catalyst crude product；
Step C: catalyst crude product is positioned in beaker standing 4h under the conditions of 25 DEG C, then catalyst crude product is put into It is dried 4h in baking oven and under the conditions of 100 DEG C, obtains NaHSO4/ MCM-50 catalyst.
Embodiment 8
The present embodiment provides a kind of at supercritical N2The NaHSO of preparation in environment4/ FSM-16 catalyst, its preparation process is such as Under:
Step A: by 0.547g NaHSO in reactor4It is dissolved in the deionized water of 2.4ml, is uniformly mixed and obtains NaHSO4Aqueous solution, by 1g FSM-16 carrier impregnation in above-mentioned NaHSO4In aqueous solution, it is uniformly mixed and obtains slurry；
Step B: with high pressure syringe pump by N2Gas is filled with reactor, and in making still, pressure reaches 10MPa, then uses program Heating up and reactor temperature is raised to 20 DEG C, to reach super critical condition, then maintain super critical condition 4h, first supercritical processing is complete Bi Hou, cooling, pressure release, unload still, obtain catalyst crude product；
Step C: catalyst crude product is positioned in beaker standing 4h under the conditions of 25 DEG C, then catalyst crude product is put into It is dried 3h 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 using conventional impregnation to prepare4/ MCM-41 catalyst, its preparation process is such as Under:
Step A: by 0.177g NaHSO in beaker4It is dissolved in the deionized water of 2.4ml, is uniformly mixed and obtains NaHSO4Aqueous solution, then by 1g MCM-41 carrier impregnation in above-mentioned solution NaHSO4In aqueous solution, supersound process 2h, it is catalyzed Agent crude product；
Step B: catalyst crude product is stood at 20 DEG C 8h, then catalyst crude product is put in baking oven and at 90 DEG C of bars It is dried 4h under part, obtains NaHSO4/ MCM-41 catalyst.
Comparative example 2
This comparative example provides a kind of NaHSO using conventional impregnation to prepare4/ MCM-41 catalyst, its preparation process is such as Under:
Step A: by 0.25g NaHSO in beaker4It is dissolved in the deionized water of 2.4ml, is uniformly mixed and obtains NaHSO4Aqueous solution, then by 1g MCM-41 carrier impregnation in above-mentioned solution NaHSO4In aqueous solution, supersound process 2h, it is catalyzed Agent crude product；
Step B: catalyst crude product is stood at 20 DEG C 4h, then catalyst crude product is put in baking oven and at 110 DEG C Under the conditions of be dried 8h, obtain NaHSO4/ MCM-41 catalyst.
Comparative example 3
This comparative example provides a kind of NaHSO using conventional impregnation to prepare4/ MCM-41 catalyst, its preparation process is such as Under:
Step A: by 0.333g NaHSO in beaker4It is dissolved in the deionized water of 2.4ml, is uniformly mixed and obtains NaHSO4Aqueous solution, then by 1g MCM-41 carrier impregnation in above-mentioned solution NaHSO4In aqueous solution, supersound process 2h, it is catalyzed Agent crude product；
Step B: catalyst crude product is stood at 25 DEG C 12h, then catalyst crude product is put in baking oven and at 100 DEG C Under the conditions of be dried 11h, obtain NaHSO4/ MCM-41 catalyst.
Comparative example 4
This comparative example provides a kind of NaHSO using conventional impregnation to prepare4/ MCM-41 catalyst, its preparation process is such as Under:
Step A: by 0.429g NaHSO in beaker4It is dissolved in the deionized water of 2.4ml, is uniformly mixed and obtains NaHSO4Aqueous solution, then by 1g MCM-41 carrier impregnation in above-mentioned solution NaHSO4In aqueous solution, supersound process 2h, it is catalyzed Agent crude product；
Step B: catalyst crude product is stood at 30 DEG C 6h, then catalyst crude product is put in baking oven and at 120 DEG C Under the conditions of be dried 10h, obtain NaHSO4/ MCM-41 catalyst.
Comparative example 5
This comparative example provides a kind of NaHSO using conventional impregnation to prepare4/ MCM-41 catalyst, its preparation process is such as Under:
Step A: by 0.538g NaHSO in beaker4It is dissolved in the deionized water of 2.4ml, is uniformly mixed and obtains NaHSO4Aqueous solution, then by 1g MCM-41 carrier impregnation in above-mentioned solution NaHSO4In aqueous solution, supersound process 2h, it is catalyzed Agent crude product；
Step B: catalyst crude product is stood at 25 DEG C 10h, then catalyst crude product is put in baking oven and at 80 DEG C Under the conditions of be dried 6h, obtain NaHSO4/ MCM-41 catalyst.
Application examples
Use fixed bed reactors, add 0.5g support type NaHSO4Catalyst, using pure Oleum Ricini as raw material, in reaction Temperature 230 DEG C, mass space velocity 0.7h-1Under test, be individually for portion according to the dehydrated castor oil obtained for each hour, with To many parts of different iodine numbers and the dehydrated castor oil of hydroxyl value.
Experimental example
Use the support type NaHSO that embodiment 1-8 is prepared with the method for comparative example 1-54Catalyst is dehydrated as Oleum Ricini Catalyst in reaction, and test its catalytic effect in Oleum Ricini dehydration.Experiment uses fixed bed reactors, with pure Oleum Ricini is as raw material, support type NaHSO4Catalyst amount 0.5g, reaction temperature is 230 DEG C, and mass space velocity is 0.7h-1Under enter OK, and to the indices of the dehydrated castor oil obtained test.
1, the iodine number of dehydrated castor oil is tested according to GB/T 5532-2008 " mensuration of animal and plant fat iodine number ", surveys Test result is shown in Table 1；
2, the hydroxyl value of dehydrated castor oil " imports and exports animal and plant fat hydroxyl value detection method " according to SN/T 0801.20-1999 Testing, test result is shown in Table 1；
3, ICP method is used to measure support type NaHSO4Sulfur content A before catalyst reaction.After reaction terminates, take out load Type NaHSO4Catalyst, uses ICP method to measure support type NaHSO after drying4Sulfur content B of catalyst.Then according to following formula calculates Go out support type NaHSO4The turnover rate of catalyst, turnover rate=(sulfur content A-sulfur content B)/sulfur content A*100%, result of calculation It is shown in Table 1.
Table 1. dehydrated castor oil indices testing result
As it can be seen from table 1 the support type NaHSO that the method for embodiment of the present invention 1-8 prepares4Catalyst with by tradition The support type NaHSO that infusion process prepares4Catalyst (comparative example 1-5) is compared, and the effect of catalytic reaction is more excellent.Specifically, exist In the reaction of Oleum Ricini dehydration, react initial 1h, use the one that embodiment of the present invention 1-8 provides at supercritical N2In environment The support type NaHSO of preparation4The dehydrated castor oil that catalyst obtains and the support type NaHSO using conventional impregnation to prepare4Catalysis The iodine number of the dehydrated castor oil that agent (comparative example 1-5) obtains and hydroxyl value are suitable, and when reaction proceeds to 10h, use 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 provided4Catalyst rear loss of active component rate before the reaction is low, so that this catalyst can be long-time Keep the catalysis of Oleum Ricini dehydration activity.
Embodiments described above is a part of embodiment of the present invention rather than whole embodiments.The reality of the present invention The detailed description executing example is not intended to limit the scope of claimed invention, but is merely representative of the selected enforcement of the present invention Example.Based on the embodiment in the present invention, those of ordinary skill in the art are obtained under not making creative work premise Every other embodiment, broadly falls into the scope of protection of the invention.

Claims (10)

1. a support type NaHSO4The preparation method of catalyst, it is characterised in that it comprises the following steps:
Carrier material be impregnated in NaHSO4In aqueous solution, it is uniformly mixing to obtain slurry；Described slurry is placed in N2Environment In, intensification, supercharging make N2Reach super critical condition persistently 2～12h, then obtain catalyst crude product through cooling, pressure release, described super Critical condition is temperature 20～80 DEG C, pressure 4～12MPa；Described catalyst crude product is dried, obtains described support type NaHSO4 Catalyst.
Preparation method the most according to claim 1, it is characterised in that described super critical condition is temperature 40～80 DEG C, pressure Strong 8～10MPa.
Preparation method the most according to claim 1, it is characterised in that described NaHSO4Mass ratio with described carrier material It is 0.173～0.547:1.
Preparation method the most according to claim 1, it is characterised in that described NaHSO4Mass ratio with described carrier material It is 0.429～0.538:1.
Preparation method the most according to claim 1, it is characterised in that described carrier material is MCM-41, MCM-48, MCM- At least one in 50 and FSM-16.
Preparation method the most according to claim 5, it is characterised in that described catalyst crude product the most also includes standing Step, the condition of described standing step is to stand 2～12h at 20～30 DEG C.
Preparation method the most according to claim 6, it is characterised in that the drying condition of described catalyst crude product be 80～ 3～12h it are dried at 120 DEG C.
8. a support type NaHSO4Catalyst, it is characterised in that use the preparation method described in claim 1-7 any one Prepare.
Support type NaHSO the most according to claim 84Catalyst, it is characterised in that described support type NaHSO4Catalyst In, described NaHSO4Load capacity be 10～70wt%.
10. a support type NaHSO as claimed in claim 84Catalyst prepares answering in dehydrated castor oil in Oleum Ricini dehydration With.
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Cited By (2)

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CN107649144A (en) * 2017-10-23 2018-02-02 李俊霞 A kind of preparation method of novel denitration catalyst
CN115672404A (en) * 2022-10-27 2023-02-03 滁州学院 Heteropolyacid (salt) @ Zr-MOFs catalyst, preparation method and application thereof

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