CN102698742A - 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 platinum (Pt) is supported on the surface of the carrier so that the Pt/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, but color lake organic pigments such as the red 36b of bright red, the new treasured of synthetic plastic, bronze red c, and this pigment is widely used in paint, coating, colored ink, rubber, coloring plastic etc.The total productive capacity of world CLT acid has at present reached 23600 tons/year, and wherein China is the country of CLT acid production ability maximum in the world, accounts for 44.9% of world's total productive capacity.
Over nearly 20 years; The CLT acid industry of China has obtained significant progress; Be that output, quality all have increased significantly, the production Technology of product is day by day ripe, and synthesis yield is greatly improved; Production cost of products reduces gradually, has certain occupation rate of market in the international market.But also there is the deficiency of a lot of aspects in the industrial expansion of CLT acid at present, and serious like environmental pollution, technology falls behind, and unstable product quality, production capacity surplus cause competitively making a price reduction etc.Problem of environmental pollution particularly makes world developed country successively close down part producing equipment or limits output that China also has enterprise to be forced to stop production because of pollution problem.The producer of domestic production CLT acid at present mainly contains Hebei Qin Yan chemical industry Co., Ltd, Qingdao Tianyuan chemical industry Co., Ltd, Jiization Liaoyuan chemical industry one factory, Weifang great achievement chemical industry Co., Ltd etc.; Wherein the production capacity of Hebei Qin Yan chemical industry Co., Ltd is maximum; Be 5000 tons/year, but problems such as environmental pollution are limiting its development always.
The synthetic route of CLT acid is a lot, mainly contains toluene sulfonation route, chlorotoluene bromination route, the nitrated route of ortho-chlorotolu'ene, meta-aminotoluene route etc.Be main with the toluene sulfonation route during at present domestic industry is produced; Be that toluene is obtained 6-chloro-3-nitrotoleune-4-azochlorosulfonate acid liquid through sulfonation, chlorination, nitrated, neutralization in the concentrated sulfuric acid; Be that catalyst is with its hydrogenating reduction with iron powder etc. then; Through neutralization, filtration, use hydrochloric acid acid out, dry sediment at last again, obtain finished product CLT acid.These method raw material sources are rich and easy to get, technical maturity, and cost is lower.But; There are many defectives with iron powder as catalyst reduction 6-chloro-3 nitrotoleunes-4-sulfonic acid; Like etching apparatus, three-waste pollution serious (iron mud amount is big), reduction yield are low, and product purity is low, iron content highly is difficult to reach export standard, influence 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.
It is the method that raw material directly carries out the nitrated CLT of preparation acid with the ortho-chlorotolu'ene that document Chinese patent CN201010252894.5 has introduced a kind of.This method at first is that catalyst, acetyl nitrate are nitrating agent with the acidic beta zeolite, obtains the itrated compound of ortho-chlorotolu'ene; Then the itrated compound of ortho-chlorotolu'ene is used iron powder reducing, and with the reduzate recrystallization, 6-chloro-3-amino toluene crystal is isolated in acid extractants; Carry out sulfonation at 170-190 ℃ with dichloro-benzenes and sulfuric acid at last and obtain CLT acid.This method technology is simple, lower to equipment requirements, and yield is high, but course of reaction is still used iron powder reducing, and cost is high, 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, the noble metal load capacity 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 platinum (Pt), and the load quality of active constituent Pt 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 carrier surface and distributes, and its Pt 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 Pt 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 platinum acid chloride 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 Pt/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 Pt, as preferably, metal Pt 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 Pt, and active component Pt 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 500 ℃, was cooled to room temperature then, and wherein the purity of Raschig ring type aluminium oxide is 95.5%, 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 2 milliliters of platinum acid chloride solutions; Be dissolved in water, add 10 milliliters of sodium hydrate aqueous solutions again, 80 ℃ of following constant temperature dippings reaction 2 hours; Calcined 2 hours down at 500 ℃ with water washing, oven dry back then, obtain product;
(3) product that step (2) is obtained is reduced in 50 milliliters hydrazine hydrate aqueous solution; Wash at last, dry, obtain finished catalyst, wherein active component Pt 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 Pt/Al continuously
2O
3Beds carries out hydrogenation reduction, be 1 hour sample time after, sampling CLT reducing solution from system.
With liquid-phase chromatographic analysis, its reaction conversion ratio is 85.6% with the sampled sample of above-mentioned CLT reducing solution, and dechlorination thing proportion is 0.5%.
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 Pt; And active component Pt is eggshell shape and distributes being Raschig ring type alumina surface, in addition in the carrier also load add auxiliary agent Na
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 sodium carbonate in the product that step (2) is obtained, in 50 milliliters hydrazine hydrate aqueous solution, reduce then; Wash at last, dry, obtain finished catalyst, wherein active component Pt quality accounts for 0.2% of Raschig ring type aluminium oxide quality, Na
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 93.5% with the sampled sample of above-mentioned CLT reducing solution, and dechlorination thing proportion is 0.5%.
Embodiment 3:
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 Pt; And active component Pt 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) the Raschig ring type aluminium oxide of getting 0.098 mole was calcined 1.5 hours at 600 ℃, was cooled to room temperature then, and wherein the purity of Raschig ring type aluminium oxide is 99.6%, and specific area is 142 meters
2/ gram, pore volume are 0.6 milliliter/gram carrier;
(2) the Raschig ring type aluminium oxide after step (1) processing is mixed with 2 milliliters of platinum acid chloride solutions, be dissolved in water, add 10 milliliters of sodium hydrate aqueous solutions again,, use water washing, drying then, obtain product 80 ℃ of following constant temperature dippings reaction 2 hours;
(3) add 0.5 milliliter of potash in the product that step (2) is obtained, in 50 milliliters hydrazine hydrate aqueous solution, reduce then; Wash at last, dry, obtain finished catalyst, wherein active component Pt 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 95.6% with the sampled sample of above-mentioned CLT reducing solution, and dechlorination thing proportion is 0.5%.
Embodiment 4:
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 Pt; And active component Pt is eggshell shape and distributes being Raschig ring type alumina surface, in addition in the carrier also load add auxiliary agent SiO
2It below is the concrete preparation process of this catalyst.
(1) the Raschig ring type aluminium oxide of getting 0.098 mole was calcined 1 hour at 700 ℃, was cooled to room temperature then, and wherein the purity of Raschig ring type aluminium oxide is 98.8%, and specific area is 145 meters
2/ gram, pore volume are 0.6 milliliter/gram carrier;
(2) the Raschig ring type aluminium oxide after step (1) processing is mixed with 2 milliliters of platinum acid chloride solutions, be dissolved in water, add 10 milliliters of sodium hydrate aqueous solutions again,, use water washing, drying then, obtain product 80 ℃ of following constant temperature dippings reaction 2 hours;
(3) add 0.5 milliliter of silicic acid in the product that step (2) is obtained, in 50 milliliters hydrazine hydrate aqueous solution, reduce then; Wash at last, dry, obtain finished catalyst, wherein active component Pt quality accounts for 0.2% of Raschig ring type aluminium oxide quality, SiO
2Quality 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 94.1% with the sampled sample of above-mentioned CLT reducing solution, and dechlorination thing proportion is 0.4%.
Embodiment 5:
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 Pt; And active component Pt is eggshell shape and distributes being Raschig ring type alumina surface, in addition in the carrier also load add auxiliary agent Na
2O.It below is the concrete preparation process of this catalyst.
(1) the Raschig ring type aluminium oxide of getting 0.098 mole was calcined 1 hour at 800 ℃, was cooled to room temperature then, and wherein the purity of Raschig ring type aluminium oxide is 95.5%, 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 3 milliliters of platinum acid chloride solutions, be dissolved in water, add 10 milliliters of sodium hydrate aqueous solutions again,, use water washing, drying then, obtain product 80 ℃ of following constant temperature dippings reaction 2 hours;
(3) add 0.5 milliliter of sodium carbonate in the product that step (2) is obtained, in 50 milliliters hydrazine hydrate aqueous solution, reduce then; Wash at last, dry, obtain finished catalyst, wherein active component Pt quality accounts for 0.3% of Raschig ring type aluminium oxide quality, and the sodium oxide molybdena 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 93.7% with the sampled sample of above-mentioned CLT reducing solution, and dechlorination thing proportion is 0.3%.
Embodiment 6:
In the present embodiment; Being used for the 6-chloro-3-nitrotoleune-catalyst of 4-azochlorosulfonate acid liquid phase hydrogenation reduction is to be carrier with the ball-aluminium oxide; At its area load active component Pt, and active component Pt is eggshell shape and distributes on the ball-aluminium oxide surface, in addition in the carrier also load add auxiliary agent Na
2O.It below is the concrete preparation process of this catalyst.
(1) ball-aluminium oxide of getting 0.098 mole was calcined 1.5 hours at 500 ℃, was cooled to room temperature then, and wherein the purity of ball-aluminium oxide is 98.5%, and specific area is 110 meters
2/ gram, pore volume are 0.5 milliliter/gram carrier;
(2) ball-aluminium oxide after step (1) processing is mixed with 4 milliliters of platinum acid chloride solutions, be dissolved in water, add 10 milliliters of sodium hydrate aqueous solutions again,, use water washing, drying then, obtain product 80 ℃ of following constant temperature dippings reaction 2 hours;
(3) add 1 milliliter of sodium carbonate in the product that step (2) is obtained, in 50 milliliters hydrazine hydrate aqueous solution, reduce then; Wash at last, dry, obtain finished catalyst, wherein active component Pt quality accounts for 0.4% of ball-aluminium oxide quality, Na
2The O quality accounts for 0.1% of ball-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 96.6% with the sampled sample of above-mentioned CLT reducing solution, and dechlorination thing proportion is 0.3%.
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 porous round alumina; At its area load active component Pt; And active component Pt is eggshell shape and distributes on porous round alumina surface, goes back load in addition in the carrier and adds auxiliary agent Na
2O.It below is the concrete preparation process of this catalyst.
The porous round alumina of (1) getting 0.098 mole was calcined 1.5 hours at 500 ℃, was cooled to room temperature then, and wherein the purity of porous round alumina is 98.5%, and specific area is 110 meters
2/ gram, pore volume are 0.5 milliliter/gram carrier;
(2) the porous round alumina after step (1) processing is mixed with 5 milliliters of platinum acid chloride solutions, be dissolved in water, add 10 milliliters of sodium hydrate aqueous solutions again,, use water washing, drying then, obtain product 80 ℃ of following constant temperature dippings reaction 2 hours;
(3) add 10 milliliters of sodium carbonate in the product that step (2) is obtained, in 50 milliliters hydrazine hydrate aqueous solution, reduce then; Wash at last, dry, obtain finished catalyst, wherein active component Pt quality accounts for 0.5% of porous round alumina quality, Na
2The O quality accounts for 1% of porous round alumina 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 97.5% with the sampled sample of above-mentioned CLT reducing solution, and dechlorination thing proportion is 0.4%.
Embodiment 8:
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 cloverleaf pattern aluminium oxide; At its area load active component Pt; And active component Pt is eggshell shape at the cloverleaf pattern alumina surface and distributes, and goes back load in addition in the carrier and adds auxiliary agent Na
2O.It below is the concrete preparation process of this catalyst.
(1) the cloverleaf pattern aluminium oxide of getting 0.098 mole was calcined 1.5 hours at 500 ℃, was cooled to room temperature then, and wherein the purity of cloverleaf pattern aluminium oxide is 99.5%, and specific area is 109 meters
2/ gram, pore volume are 0.4 milliliter/gram carrier;
(2) the cloverleaf pattern aluminium oxide after step (1) processing is mixed with 5 milliliters of platinum acid chloride solutions, be dissolved in water, add 10 milliliters of sodium hydrate aqueous solutions again,, use water washing, drying then, obtain product 80 ℃ of following constant temperature dippings reaction 2 hours;
(3) add 10 milliliters of sodium carbonate in the product that step (2) is obtained, in 50 milliliters hydrazine hydrate aqueous solution, reduce then; Wash at last, dry, obtain finished catalyst, wherein active component Pt quality accounts for 0.5% of cloverleaf pattern aluminium oxide quality, Na
2The O quality accounts for 1% of cloverleaf pattern 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 95.5% with the sampled sample of above-mentioned CLT reducing solution, and dechlorination thing proportion is 0.4%
Embodiment 9:
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 cloverleaf pattern aluminium oxide; At its area load active component Pt; And active component Pt is eggshell shape at the cloverleaf pattern alumina surface and distributes, and goes back load in addition in the carrier and adds auxiliary agent Na
2O.It below is the concrete preparation process of this catalyst.
(1) the cloverleaf pattern aluminium oxide of getting 0.098 mole was calcined 1.5 hours at 500 ℃, was cooled to room temperature then, and wherein the purity of cloverleaf pattern aluminium oxide is 99.5%, and specific area is 109 meters
2/ gram, pore volume are 0.4 milliliter/gram carrier;
(2) the cloverleaf pattern aluminium oxide after step (1) processing is mixed with 5 milliliters of platinum acid chloride solutions, be dissolved in water, add 10 milliliters of sodium hydrate aqueous solutions again,, use water washing, drying then, obtain product 80 ℃ of following constant temperature dippings reaction 2 hours;
(3) add 20 milliliters of sodium carbonate in the product that step (2) is obtained, in 50 milliliters hydrazine hydrate aqueous solution, reduce then; Wash at last, dry, obtain finished catalyst, wherein active component Pt quality accounts for 0.5% of cloverleaf pattern aluminium oxide quality, Na
2The O quality accounts for 2% of cloverleaf pattern 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 96.2% with the sampled sample of above-mentioned CLT reducing solution, and dechlorination thing proportion is 0.3%
Embodiment 10:
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 Pt; And active component Pt is eggshell shape and distributes being Raschig ring type alumina surface, in addition in the carrier also load add auxiliary agent Na
2O.It below is the concrete preparation process of this catalyst.
(1) the Raschig ring type aluminium oxide of getting 0.098 mole was calcined 1.5 hours at 500 ℃, was cooled to room temperature then, and wherein the purity of Raschig ring type aluminium oxide is 95.5%, 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 10 milliliters of platinum acid chloride solutions, be dissolved in water, add 10 milliliters of sodium hydrate aqueous solutions again,, use water washing, drying then, obtain product 80 ℃ of following constant temperature dippings reaction 2 hours;
(3) add 0.5 milliliter of sodium carbonate in the product that step (2) is obtained, in 50 milliliters hydrazine hydrate aqueous solution, reduce then; Wash at last, dry, obtain finished catalyst, wherein active component Pt quality accounts for 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, 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 99.8% with the sampled sample of above-mentioned CLT reducing solution, and dechlorination thing proportion is 0.2%.
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 platinum, and the load quality of described active constituent metal platinum 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 platinum 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 platinum 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 platinum 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 platinum acid chloride 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 or 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 platinum acid chloride 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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| CN102964278A (en) * | 2012-11-27 | 2013-03-13 | 浙江秦燕化工有限公司 | Method for preparing CLT acid (2-amino-4-methyl-5-chlorobenzene sulfonic acid) by continuous catalytic hydrogenation reduction |
| CN110538651A (en) * | 2019-09-10 | 2019-12-06 | 沈阳化工研究院有限公司 | Platinum-carbon catalyst and preparation method thereof |
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Cited By (3)
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| CN102964278B (en) * | 2012-11-27 | 2015-02-18 | 浙江秦燕化工有限公司 | Method for preparing CLT acid (2-amino-4-methyl-5-chlorobenzene sulfonic acid) by continuous catalytic hydrogenation reduction |
| CN110538651A (en) * | 2019-09-10 | 2019-12-06 | 沈阳化工研究院有限公司 | Platinum-carbon catalyst and preparation method thereof |
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