CN102698743A - Catalyst for liquid-phase hydrogenation reduction reaction of 6-chloro-3-nitrotoluene-4-sulfonic acid (CLT acid) and method for preparing same - Google Patents
Catalyst for liquid-phase hydrogenation reduction reaction of 6-chloro-3-nitrotoluene-4-sulfonic acid (CLT acid) and method for preparing same Download PDFInfo
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Abstract
The invention provides a catalyst for the liquid-phase hydrogenation reduction reaction of 6-chloro-3-nitrotoluene-4-sulfonic acid (CLT acid) and a method for preparing the catalyst. The alumina (Al2O3) in the columnar structure or spherical structure is used as the carrier, and the active component which is the palladium (Pd) is supported on the surface of the carrier so that the Pd/Al2O3 catalyst preferentially distributed like an eggshell is formed, wherein the mass of the platinum is 0.05-10% of that of the carrier. Compared with the prior art, the catalyst provided by the invention has good hydrogenation activity, high selectivity and low dechlorination. When the catalyst is used for the hydrogenation reduction and the production of the CLT acid, high reduction rate is achieved, the product has good purity, and less pollution is caused to the environment.
Description
Technical field
The present invention relates to CLT technic acid field, relate in particular to the Catalysts and its preparation method of a kind of 6-of being used for chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid phase hydrogenation reduction.
Background technology
6-chloro-3-amino toluene-4-sulfonic acid, its English name is 6-chloro-3-nitrotoluene-4-sulfonic acid, is called for short CLT acid.CLT acid is a kind of important organic red pigment intermediate, on pigment industry, is mainly used in to produce C.I. paratonere 52 and C.I. paratonere 53, and this pigment is widely used in aspects such as paint, coating, colored ink, rubber and coloring plastic.
The synthetic route of CLT acid has a lot, mainly contains according to the raw material difference:
(1) toluene sulfonation route: it is rich and easy to get that this route has raw material sources, advantage such as technical maturity, cost are lower; But reaction scheme is long, operation is many, and the reaction isomers is many, and total recovery has only about 50%, and the course of reaction quantity of three wastes is big in addition, is difficult to handle;
(2) ortho-chlorotolu'ene bromination route; The advantage of this route is that yield is higher, and quantity of three wastes is few, but higher to equipment requirements, needs to press hot axe and bromine retracting device, causes production cost higher;
(3) the nitrated route of ortho-chlorotolu'ene: this route technology is simple, quantity of three wastes is few, but nitrated yield is low, only reaches about about 40%;
(4) meta-aminotoluene route: be to obtain two (tolyl) urea by meta-aminotoluene and phosgene reaction; Two (tolyl) urea obtains chlorination two (tolyl) urea through superchlorination; The latter obtains CLT acid through oversulfonate, hydrolysis, and its synthetic total recovery is about 62～65%.
At present, the toluene sulfonation route is generally adopted in suitability for industrialized production CLT acid both at home and abroad.This route is, and to be raw material with toluene obtain 6-chloro-3 nitrotoleunes-4-sulfonic acid through sulfonation, chlorination, nitrated, 4 steps of saltouing, and under the catalyst condition, 6-chloro-3 nitrotoleunes-4-sulfonic acid hydrogenating reduction produced CLT acid then.Wherein, be used for the sour catalyst of itrated compound hydrogenation preparing CLT on the commercial production iron powder, Pd/C are arranged.With the iron powder be catalyst hydrogenation also original production CLT acid have many defectives, like etching apparatus, three-waste pollution serious (iron mud amount is big), reduction yield are low, product purity is low, iron content is high is difficult to reach export standard, influences economic benefit etc.
In addition, present above-mentioned 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid phase hydrogenation reduction normally adopts intermittent reaction to accomplish in agitated reactor, and have following problem: (one) agitated reactor volume is bigger; (2) there is process such as stirring in the reaction, causes the mechanical wear of catalyst granules to some extent; (3) reaction stability is poor, dechlorination is high, and selectivity is low, side reaction is more; (4) need the catalyst recovery aftertreatment technology, have that catalyst activity component loss loss is big, catalyst life is short; (5) catalyst even corrosion reacting kettle such as iron produces problems such as environmental pollution.
The publication number of Yanbian University is the technology that the Chinese invention patent application of CN101219977A discloses a kind of CLT of being used for acid hydrogenation; With iron powder as catalyst for hydrogenation; Through waste liquid circulation and concentrate and burn the processing pollution problem; But the processing method of not mentioned a large amount of catalyst waste material iron mud, final yield is not high yet.
The publication number of Yanbian University is that the Chinese invention patent application of CN101906057A discloses-method of method for preparing CLT acid (6-chloro-3-aminotoluene-4-sulfoacid) by utilizing o-chlorotoluene direct nitrification, and wherein catalyst is that acid zeolite, nitrating agent are the acetyl nitrate, obtain the itrated compound of ortho-chlorotolu'ene; Use iron powder reducing again, separating purifies obtains finished product.This method equipment requirements is low, high yield, but still use iron powder reducing, and cost is high, and residue contamination is big, and is intermittent reaction, has the catalyst treatment problem.
Summary of the invention
Technical purpose of the present invention is to producing with the toluene sulfonation route in the process of CLT acid; Problems such as the reduction yield that when adopting iron powder etc. as catalyst reduction 6-chloro-3 nitrotoleunes-4-sulfonic acid, is produced is low, product purity is low and environmental pollution is serious; The new catalyst that is used for 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid phase hydrogenation reduction in a kind of CLT acid production process is provided; This catalyst has the advantage that hydrogenation activity is good, selectivity is high, dechlorination is low, high, the good product purity and low in the pollution of the environment of percent reduction when using this catalyst reduction 6-chloro-3 nitrotoleunes-4-sulfonic acid.
The present invention realizes that the technical scheme that above-mentioned technical purpose is taked is: the catalyst of a kind of 6-of being used for chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid phase hydrogenation reduction; With column structure aluminium oxide or spherical structure aluminium oxide is carrier; In its area load active constituent Metal Palladium (Pd), and the load quality of active constituent Pd accounts for 0.05% ~ 10% of carrier quality.
In the technique scheme:
The cross section of described column structure aluminium oxide includes but not limited to circle, single hole is circular, porous is circular or cloverleaf pattern.
Described active component Pd is eggshell type at Raschig ring shape alumina carrier surface and distributes, and its Pd shell thickness is preferably 0.01 millimeter ~ 1 millimeter, further is preferably 0.05 millimeter ~ 0.5 millimeter.
It is 0.08% ~ 5% that the load quality of described active component Pd accounts for the carrier quality optimization, is preferably 0.1% ~ 2.5% again, further is preferably 0.15% ~ 2%, most preferably is 0.18% ~ 0.48%.
The purity of described carrier is preferably 80 ~ 99.99%.
The specific area of described carrier is preferably 50 meters
2~ 240 meters of/grams
2/ gram, pore volume are preferably 0.3 milliliter/gram carrier ~ 1.2 milliliter/gram carrier.
As preferably, add auxiliary agent Na in the described catalyst in addition
2O, K
2O or SiO
2, described interpolation auxiliary agent quality accounts for 0.05% ~ 2% of carrier quality, further is preferably 0.06% ~ 1%.
The Preparation of catalysts method that the present invention is used for 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid phase hydrogenation reduction comprises the steps:
Step 1: an amount of column structure aluminium oxide or spherical structure aluminium oxide were calcined 1 ~ 6 hour at 200 ℃ ~ 1000 ℃, be cooled to room temperature then, obtain alumina catalyst support;
Step 2: the alumina catalyst support that step 1 is obtained is immersed in the mixed solution that the aqueous solution by an amount of chlorine palladium acid solution and NaOH, potassium hydroxide, lithium hydroxide or magnesium hydroxide forms; 50 ~ 200 ℃ of following isothermal reactions 0.1 ~ 4 hour; Washing, dry back were 350 ~ 600 ℃ of roastings 3 ~ 12 hours; With reducing agent reduction, washing, drying, obtain finished catalyst again.
Catalyst of the present invention can be used for 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid phase hydrogenating reduction and prepare CLT acid; Can be employed in agitated reactor discontinuous formula prepared in reaction CLT acid during concrete preparation, also can be employed in and carry out continuous reaction in the fixed bed reactors and prepare CLT acid.As preferably; Be employed in continuous reaction and prepare CLT acid, this method is in fixed bed reactors, uses above-mentioned catalyst; Liquid phase 6-chloro-3-nitrotoleune-4-sulfonic acid and hydrogen are carried out hydrogenating reduction with the mode of continuous feed, discharging through catalyst, obtain CLT acid.
The above-mentioned preparation in the sour method of CLT:
Described liquid phase 6-chloro-3-nitrotoleune-4-sulfonic acid includes but not limited to the aqueous solution or the salting liquid of 6-chloro-3-nitrotoleune-4-sulfonic acid, and wherein the salting liquid of 6-chloro-3-nitrotoleune-4-sulfonic acid includes but not limited to lithium salts, sodium salt, sylvite, magnesium salts or the calcium salt of 6-chloro-3-nitrotoleune-4-sulfonic acid.The described liquid phase 6-chloro-3-solvent that nitrotoleune-4-sulfonic acid is selected for use includes but not limited to water, methyl alcohol, ethanol or acetone.
The weight percent concentration of described liquid phase 6-chloro-3-nitrotoleune-4-sulfonic acid is preferably 1%-20%.
Described liquid phase 6-chloro-3-nitrotoleune-4-sulfonic acid can adopt with the continuous feed of measuring pump mode, and charging rate is preferably 0.01-0.1 milliliter/(minute * milliliter catalyst);
Described hydrogen feeds in the reactor continuously, and the pressure of hydrogen is preferably 1～30MPa, hydrogen feed speed be preferably 0.01～1 milliliter/(minute * milliliter catalyst);
Described fixed bed reaction actuator temperature preferably is set to 20～300 ℃, further is preferably 30～250 ℃.
In order to improve the catalytic reduction reaction effect,, before liquid phase 6-chloro-3-nitrotoleune-4-sulfonic acid charging, at first adopt hydrogen with Pd/Al as preferably
2O
3Catalyst was 50～500 ℃ of reduction 0.50～10 hour;
In sum; It is carrier that the catalyst of the 6-of being used for chloro-3-nitrotoleune provided by the invention-4-azochlorosulfonate acid liquid phase hydrogenation reduction is selected column structure aluminium oxide or spherical structure aluminium oxide for use; At its area load active constituent metal Pd, as preferably, metal Pd is eggshell shape at carrier surface and distributes.Experiment confirm; Use catalyst of the present invention can in actual catalytic reduction reaction process, effectively reduce deep reaction; Improve the catalytic activity of catalyst, thereby improve the hydrogenation reduction conversion ratio, wherein in fixed bed reactors, carry out 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid mutually continuously during hydrogenation reduction the reduction conversion ratio up to 99.8%; And dechlorination is very low, the advantage that have the catalyst long service life, can reuse, environmental pollution is low.
The specific embodiment
Below in conjunction with specific embodiment the present invention is described further, it is pointed out that the following stated embodiment is intended to be convenient to understanding of the present invention, and it is not played any qualification effect.
Embodiment 1:
In the present embodiment; The catalyst that is used for 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid phase hydrogenation reduction is to be carrier with Raschig ring type (being that single hole is cylindrical) aluminium oxide; At its area load active component Pd, and active component Pd is the distribution of eggshell shape at Raschig ring type alumina surface.It below is the concrete preparation process of this catalyst.
(1) the Raschig ring type aluminium oxide of getting 0.098 mole was calcined 2 hours at 300 ℃, was cooled to room temperature then, and wherein the purity of Raschig ring type aluminium oxide is 99.5%, and specific area is 103 meters
2/ gram, pore volume are 0.5 milliliter/gram carrier;
(2) the Raschig ring type aluminium oxide after step (1) processing is mixed with 4 milliliters of chlorine palladium acid solutions (containing 4 milligrams of element palladiums); Be dissolved in water; Add 10 milliliters of sodium hydrate aqueous solutions (containing 0.0078 mole in NaOH) again; Flood reaction 2 hours at 80 ℃ of following constant temperature, calcined 2 hours down at 300 ℃ with water washing, oven dry back then, obtain product;
(3) product that step (2) is obtained contained in 2% the hydrazine hydrate aqueous solution reduction 1 hour at 50 milliliters; Wash at last, dry, obtain finished catalyst, wherein active component Pd quality accounts for 0.2% of Raschig ring type aluminium oxide quality.
The above-mentioned catalyst for preparing is used for the continuous mutually hydrogenating reduction of 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid prepares CLT acid, it is following specifically to prepare process.
(1) in fixed bed reactors, add 200 milliliters of catalyst, with hydrogen with this catalyst at 300 ℃ of following reductase 12s hour;
(2) system is warming up to 80 ℃; System is fed hydrogen continuously; Hydrogen Vapor Pressure rises to 6MPa, is the aqueous solution of saturated 6-chloro-3-nitrotoleune-4-sulfonate sodium of 5% with the continuous input weight percentage concentration of measuring pump, input quantity be set to 0.05 milliliter/(minute * milliliter catalyst); The hydrogen input quantity be 7.5 milliliters/(minute * milliliter catalyst), make hydrogen and saturated 6-chloro-3-nitrotoleune-4-sulfonate solution pass through Pd/Al continuously
2O
3Beds carried out hydrogenation reduction 4 hours, got the CLT reducing solution.
With liquid-phase chromatographic analysis, its reaction conversion ratio is 93.5% with above-mentioned CLT reducing solution, and dechlorination thing proportion is 0.56%.
Embodiment 2:
In the present embodiment; The catalyst that is used for 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid phase hydrogenation reduction is to be carrier with Raschig ring type aluminium oxide; At its area load active component Pd; And active component Pd is eggshell shape and distributes being Raschig ring type alumina surface, in addition in the carrier also load add auxiliary agent K
2O.It below is the concrete preparation process of this catalyst.
(1) with embodiment 1 in step (1) identical;
(2) with embodiment 1 in step (2) identical;
(3) add 0.5 milliliter of K in the product that step (2) is obtained
2CO
3, contained in 2% the hydrazine hydrate aqueous solution reduction 1 hour at 50 milliliters then; Wash at last, dry, obtain finished catalyst, wherein active component Pd quality accounts for 0.2% of Raschig ring type aluminium oxide quality, K
2The O quality accounts for 0.05% of Raschig ring type aluminium oxide quality.
The above-mentioned catalyst for preparing is used for the continuous mutually hydrogenating reduction of 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid prepares CLT acid, specifically prepare process with the CLT acid preparation process among the above-mentioned embodiment 1, the CLT reducing solution of from system, taking a sample after 1 hour.
With liquid-phase chromatographic analysis, its reaction conversion ratio is 98.9% with above-mentioned CLT reducing solution, and dechlorination thing proportion is 0.55%.
Embodiment 3:
In the present embodiment, the structure and the embodiment 2 of catalyst that is used for 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid phase hydrogenation reduction is identical.It below is the concrete preparation process of this catalyst.
(1) with embodiment 2 in step (1) basic identical, Raschig ring type aluminium oxide that different is was 500 ℃ of calcinings 2 hours;
(2) with embodiment 2 in step (2) identical;
(3) with embodiment 2 in step (3) identical;
Obtain finished catalyst, wherein active component Pd quality accounts for 0.2% of Raschig ring type aluminium oxide quality, K
2The O quality accounts for 0.05% of Raschig ring type aluminium oxide quality.
The above-mentioned catalyst for preparing is used for the continuous mutually hydrogenating reduction of 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid prepares CLT acid, specifically prepare process with the CLT acid preparation process among the above-mentioned embodiment 1, the CLT reducing solution of from system, taking a sample after 1 hour.
With liquid-phase chromatographic analysis, its reaction conversion ratio is 98.6% with above-mentioned CLT reducing solution, and dechlorination thing proportion is 0.51%.
Embodiment 4:
In the present embodiment, the structure and the embodiment 2 of catalyst that is used for 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid phase hydrogenation reduction is identical.It below is the concrete preparation process of this catalyst.
(1) with embodiment 2 in step (1) basic identical, Raschig ring type aluminium oxide that different is was 800 ℃ of calcinings 2 hours;
(2) with embodiment 2 in step (2) identical;
(3) with embodiment 2 in step (3) identical;
Obtain finished catalyst, wherein active component Pd quality accounts for 0.2% of Raschig ring type aluminium oxide quality, K
2The O quality accounts for 0.05% of Raschig ring type aluminium oxide quality.
The above-mentioned catalyst for preparing is used for the continuous mutually hydrogenating reduction of 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid prepares CLT acid, specifically prepare process with the CLT acid preparation process among the above-mentioned embodiment 1, the CLT reducing solution of from system, taking a sample after 1 hour.
With liquid-phase chromatographic analysis, its reaction conversion ratio is 99.6% with above-mentioned CLT reducing solution, and dechlorination thing proportion is 0.41%.
Embodiment 5:
In the present embodiment, the structure and the embodiment 2 of catalyst that is used for 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid phase hydrogenation reduction is identical.The concrete preparation process and the concrete preparation process among the embodiment 2 of this catalyst are identical, obtain finished catalyst, and wherein active component Pd quality accounts for 0.2% of Raschig ring type aluminium oxide quality, K
2The O quality accounts for 0.05% of Raschig ring type aluminium oxide quality.
The above-mentioned catalyst for preparing is used for the continuous mutually hydrogenating reduction of 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid prepares CLT acid; CLT acid preparation process in concrete preparation process and the foregoing description 1 is basic identical; Continously hydrogen adding reduction reaction that different is in step (2) 8 hours obtains the CLT reducing solution.
With liquid-phase chromatographic analysis, its reaction conversion ratio is 99.7% with above-mentioned CLT reducing solution, and dechlorination thing proportion is 0.33%.
Embodiment 6:
In the present embodiment; The catalyst that is used for 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid phase hydrogenation reduction is to be carrier with the ball-type aluminium oxide; At its area load active component Pd, and active component Pd is eggshell shape at the ball-type alumina surface and distributes, in addition in the carrier also load add auxiliary agent K
2O.It below is the concrete preparation process of this catalyst.
(1) with embodiment 2 in step (1) basic identical, catalyst for reaction that different is is to be carrier with the ball-type aluminium oxide;
(2) with embodiment 2 in step (2) identical;
(3) with embodiment 2 in step (3) identical;
Obtain finished catalyst, wherein active component Pd quality accounts for 0.2% of ball-type aluminium oxide quality, K
2The O quality accounts for 0.05% of ball-type aluminium oxide quality.
The above-mentioned catalyst for preparing is used for the continuous mutually hydrogenating reduction of 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid prepares CLT acid, the CLT acid preparation process that specifically prepares in process and the foregoing description 1 is identical.
With liquid-phase chromatographic analysis, its reaction conversion ratio is 96.5% with above-mentioned CLT reducing solution, and dechlorination thing proportion is 0.46%.
Embodiment 7:
In the present embodiment; The catalyst that is used for 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid phase hydrogenation reduction is to be carrier with the trifolium-shaped aluminium oxide; At its area load active component Pd; And active component Pd is eggshell shape at the trifolium-shaped alumina surface and distributes, and goes back load in addition in the carrier and adds auxiliary agent K
2O.It below is the concrete preparation process of this catalyst.
(1) with embodiment 2 in step (1) basic identical, catalyst for reaction that different is is to be carrier with the trifolium-shaped aluminium oxide;
(2) with embodiment 2 in step (2) identical;
(3) with embodiment 2 in step (3) identical;
Obtain finished catalyst, wherein active component Pd quality accounts for 0.2% of trifolium-shaped aluminium oxide quality, K
2The O quality accounts for 0.05% of trifolium-shaped aluminium oxide quality.
The above-mentioned catalyst for preparing is used for the continuous mutually hydrogenating reduction of 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid prepares CLT acid, the CLT acid preparation process that specifically prepares in process and the foregoing description 1 is identical.
With liquid-phase chromatographic analysis, its reaction conversion ratio is 94.76% with above-mentioned CLT reducing solution, and dechlorination thing proportion is 0.50%.
Embodiment 8:
In the present embodiment, the structure and the embodiment 2 of catalyst that is used for 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid phase hydrogenation reduction is identical.It below is the concrete preparation process of this catalyst.
(1) with embodiment 2 in step (1) identical;
(2) with embodiment 2 in step (2) basic identical;
(3) with embodiment 2 in step (3) basic identical, the sylvite amount that different is adds is 0.1 milliliter;
Obtain finished catalyst, wherein active component Pd quality accounts for 0.2% of Raschig ring type aluminium oxide quality, K
2The O quality accounts for 0.1% of Raschig ring type aluminium oxide quality.
The above-mentioned catalyst for preparing is used for the continuous mutually hydrogenating reduction of 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid prepares CLT acid, the CLT acid preparation process that specifically prepares in process and the foregoing description 1 is identical.
With liquid-phase chromatographic analysis, its reaction conversion ratio is 93.5% with above-mentioned CLT reducing solution, and dechlorination thing proportion is 0.56%.
Embodiment 9:
In the present embodiment, the structure and the embodiment 2 of catalyst that is used for 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid phase hydrogenation reduction is identical.Concrete preparation process is basic identical in concrete preparation process and the foregoing description 8, and different is that the sylvite amount that adds is 2 milliliters;
Obtain finished catalyst, wherein active component Pd quality accounts for 0.2% of Raschig ring type aluminium oxide quality, K
2The O quality accounts for 0.2% of Raschig ring type aluminium oxide quality.
The above-mentioned catalyst for preparing is used for the continuous mutually hydrogenating reduction of 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid prepares CLT acid, the CLT acid preparation process that specifically prepares in process and the foregoing description 1 is identical.
With liquid-phase chromatographic analysis, its reaction conversion ratio is 97.96% with above-mentioned CLT reducing solution, and dechlorination thing proportion is 0.45%.
Embodiment 10:
In the present embodiment, the structure and the embodiment 2 of catalyst that is used for 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid phase hydrogenation reduction is identical.It below is the concrete preparation process of this catalyst.
(1) with embodiment 2 in step (1) identical;
(2) with embodiment 2 in step (2) basic identical, different is that chlorine palladium acid solution is 1 milliliter (containing 1 milligram of element palladium);
(3) with embodiment 2 in step (3) identical;
Obtain finished catalyst, wherein active component Pd quality accounts for 0.1% of Raschig ring type aluminium oxide quality, K
2The O quality accounts for 0.05% of Raschig ring type aluminium oxide quality.
The above-mentioned catalyst for preparing is used for the continuous mutually hydrogenating reduction of 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid prepares CLT acid, the CLT acid preparation process that specifically prepares in process and the foregoing description 1 is identical.
With liquid-phase chromatographic analysis, its reaction conversion ratio is 97.9% with above-mentioned CLT reducing solution, and dechlorination thing proportion is 0.39%.
Embodiment 11:
In the present embodiment, the structure and the embodiment 2 of catalyst that is used for 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid phase hydrogenation reduction is identical.Concrete preparation process is basic identical in concrete preparation process and the foregoing description 10, and different is that chlorine palladium acid solution is 3 milliliters (containing 3 milligrams of element palladiums); Obtain finished catalyst, wherein active component Pd quality accounts for 0.3% of Raschig ring type aluminium oxide quality, K
2The O quality accounts for 0.05% of Raschig ring type aluminium oxide quality.
The above-mentioned catalyst for preparing is used for the continuous mutually hydrogenating reduction of 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid prepares CLT acid, the CLT acid preparation process that specifically prepares in process and the foregoing description 1 is identical.
With liquid-phase chromatographic analysis, its reaction conversion ratio is 98.2% with above-mentioned CLT reducing solution, and dechlorination thing proportion is 0.37%.
Embodiment 12:
In the present embodiment, the structure and the embodiment 2 of catalyst that is used for 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid phase hydrogenation reduction is identical.Concrete preparation process is basic identical in concrete catalyst preparation process and the foregoing description 10, and different is that chlorine palladium acid solution is 4 milliliters (containing 4 milligrams of element palladiums); Obtain finished catalyst, wherein active component Pd quality accounts for 0.4% of Raschig ring type aluminium oxide quality, K
2The O quality accounts for 0.05% of Raschig ring type aluminium oxide quality.
The above-mentioned catalyst for preparing is used for the continuous mutually hydrogenating reduction of 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid prepares CLT acid, the CLT acid preparation process that specifically prepares in process and the foregoing description 1 is identical.
With liquid-phase chromatographic analysis, its reaction conversion ratio is 98.9% with above-mentioned CLT reducing solution, and dechlorination thing proportion is 0.35%.
Embodiment 13:
In the present embodiment, the structure and the embodiment 2 of catalyst that is used for 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid phase hydrogenation reduction is identical.Concrete preparation process is basic identical in concrete catalyst preparation process and the foregoing description 10, and different is that chlorine palladium acid solution is 5 milliliters (containing 5 milligrams of element palladiums); Obtain finished catalyst, wherein active component Pd quality accounts for 0.5% of Raschig ring type aluminium oxide quality, K
2The O quality accounts for 0.05% of Raschig ring type aluminium oxide quality.
The above-mentioned catalyst for preparing is used for the continuous mutually hydrogenating reduction of 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid prepares CLT acid, the CLT acid preparation process that specifically prepares in process and the foregoing description 1 is identical.
With liquid-phase chromatographic analysis, its reaction conversion ratio is 99.2% with above-mentioned CLT reducing solution, and dechlorination thing proportion is 0.33%.
Above-described embodiment specifies technical scheme of the present invention; Be understood that the above is merely specific embodiment of the present invention; Be not limited to the present invention; All any modifications of in principle scope of the present invention, being made, replenish or similar fashion substitutes etc., all should be included within protection scope of the present invention.
Claims (10)
1. the catalyst that is used for 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid phase hydrogenation reduction; It is characterized in that: with column structure aluminium oxide or spherical structure aluminium oxide is carrier; In its area load active constituent Metal Palladium, and the load quality of described active constituent Metal Palladium accounts for 0.05% ~ 10% of carrier quality.
2. the catalyst that is used for 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid phase hydrogenation reduction according to claim 1 is characterized in that: the cross section of described column structure aluminium oxide is for circle, single hole is circular, porous is circular or cloverleaf pattern.
3. the catalyst that is used for 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid phase hydrogenation reduction according to claim 1 is characterized in that: described Metal Palladium is eggshell type at carrier surface and distributes.
4. the catalyst that is used for 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid phase hydrogenation reduction according to claim 2, it is characterized in that: the shell thickness of described Metal Palladium is 0.01 millimeter ~ 1 millimeter.
5. the catalyst that is used for 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid phase hydrogenation reduction according to claim 1, it is characterized in that: the load quality of described Metal Palladium accounts for 0.08% ~ 5% of carrier quality.
6. the catalyst that is used for 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid phase hydrogenation reduction according to claim 1, it is characterized in that: the specific area of described carrier is 50 meters
2~ 240 meters of/grams
2/ gram, pore volume are 0.3 milliliter/gram carrier ~ 1.2 milliliter/gram carrier.
7. according to the described catalyst that is used for 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid phase hydrogenation reduction of arbitrary claim in the claim 1 to 6, it is characterized in that: described carrier also load adds auxiliary agent Na
2O, K
2O or SiO
2, described interpolation auxiliary agent quality accounts for 0.05 ~ 2% of carrier quality.
8. according to the described Preparation of catalysts method that is used for 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid phase hydrogenation reduction of arbitrary claim in the claim 1 to 6, it is characterized in that: comprise the steps:
Step 1: an amount of column structure aluminium oxide or spherical structure aluminium oxide were calcined 1 ~ 6 hour at 200 ℃ ~ 1000 ℃, be cooled to room temperature then, obtain alumina catalyst support;
Step 2: the alumina catalyst support that step 1 is obtained is immersed in the mixed solution that the aqueous solution by an amount of chlorine palladium acid solution and NaOH, potassium hydroxide, lithium hydroxide or magnesium hydroxide forms; 50 ~ 200 ℃ of following isothermal reactions 0.1 ~ 4 hour; Washing, dry back were 350 ~ 600 ℃ of roastings 3 ~ 12 hours; With reducing agent reduction, washing, drying, obtain finished catalyst again.
9. the Preparation of catalysts method that is used for 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid phase hydrogenation reduction according to claim 8, it is characterized in that: described reducing agent is hydrazine hydrate aqueous solution, hydrogen.
10. according to Claim 8 or the 9 described Preparation of catalysts methods that are used for 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid phase hydrogenation reduction; It is characterized in that: in the described step 2; At first in alumina catalyst support, add an amount of sodium salt, sylvite or silicate; Be immersed in again in a certain amount of mixed solution that forms by the aqueous solution of chlorine palladium acid solution and NaOH, potassium hydroxide, lithium hydroxide or magnesium hydroxide,, use water washing, dry back then 350 ~ 600 ℃ of roastings 3 ~ 12 hours 50 ~ 200 ℃ of following isothermal reactions 0.1 ~ 4 hour; With reducing agent reduction, washing, drying, obtain finished catalyst again.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103769094A (en) * | 2014-01-20 | 2014-05-07 | 中国科学院宁波材料技术与工程研究所 | Eggshell type catalyst for selective hydrogenation reaction as well as preparation method and application thereof |
| CN109651205A (en) * | 2018-12-18 | 2019-04-19 | 山东世纪阳光科技有限公司 | A kind of CLT acid synthetic method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5896056A (en) * | 1981-10-17 | 1983-06-07 | ヘキスト・アクチエンゲゼルシヤフト | Manufacture of 6-chloro-3-toluidine-4-sulfonic acid |
| CN1071443A (en) * | 1991-10-04 | 1993-04-28 | 兰州化学工业公司化工研究院 | A kind of catalyzer that is used for one-stage selective hydrogenation of gasoline splitting |
| CN101219977A (en) * | 2008-01-25 | 2008-07-16 | 延边大学 | CLT acid production method without acid waste liquid discharge |
-
2012
- 2012-05-18 CN CN201210160183.4A patent/CN102698743B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5896056A (en) * | 1981-10-17 | 1983-06-07 | ヘキスト・アクチエンゲゼルシヤフト | Manufacture of 6-chloro-3-toluidine-4-sulfonic acid |
| CN1071443A (en) * | 1991-10-04 | 1993-04-28 | 兰州化学工业公司化工研究院 | A kind of catalyzer that is used for one-stage selective hydrogenation of gasoline splitting |
| CN101219977A (en) * | 2008-01-25 | 2008-07-16 | 延边大学 | CLT acid production method without acid waste liquid discharge |
Non-Patent Citations (1)
| Title |
|---|
| 南军: "重整汽油选择性加氢Pd基催化剂的制备、表征与加氢性能", 《中国博士学位论文全文数据库 工程科技I辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103769094A (en) * | 2014-01-20 | 2014-05-07 | 中国科学院宁波材料技术与工程研究所 | Eggshell type catalyst for selective hydrogenation reaction as well as preparation method and application thereof |
| CN109651205A (en) * | 2018-12-18 | 2019-04-19 | 山东世纪阳光科技有限公司 | A kind of CLT acid synthetic method |
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