CN103170349B - A kind of carbon four that mixes is selected copper catalyst of hydrogenation and preparation method thereof - Google Patents
A kind of carbon four that mixes is selected copper catalyst of hydrogenation and preparation method thereof Download PDFInfo
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- CN103170349B CN103170349B CN201110439917.8A CN201110439917A CN103170349B CN 103170349 B CN103170349 B CN 103170349B CN 201110439917 A CN201110439917 A CN 201110439917A CN 103170349 B CN103170349 B CN 103170349B
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Abstract
The invention discloses a kind of carbon four that mixes and select copper catalyst of hydrogenation and preparation method thereof. This catalyst comprises alumina support, 5～50% active component Cu, one or more in auxiliary agent A g, the Co of 0.1～20% total content, Fe, Mn, Ni, Zn, Cr, Pd. In the preparation process of catalyst, add organic amine and metal component complexing, effectively improved uniformity and the dispersiveness of alloy that catalyst surface forms. The present invention is used for mixing carbon four and selects acetylene hydrogenation technique, and selectively good, the cycle of operation is long.
Description
Technical field
The present invention relates to a kind of selective hydrogenation catalyst and preparation method thereof. Specifically, the present invention relates to oneHydrogenation catalyst kind taking the copper alloy of even and high dispersive as active component, is specially adapted to cracking c_4 and heats up in a steamerPart selects acetylene hydrogenation to produce butadiene.
Background technology
At present, two sections of extractings, two sections of rectification process are the main stream approach of producing 1,3-butadiene. The eighties,DOW company will select hydrogenation technique to introduce the production of butadiene, i.e. KLP technology, the catalyst of use withCu is active component, adds in addition some auxiliary agents to improve the selective of Cu catalyst, and it represents that patent isUS4101451. Cu catalyst selectively good, subject matter is that the single cycle of operation is short, needs frequent regeneration.The whole world only has a few cover butadiene product equipments using KLP technology.
In recent years, Pd catalyst became the main direction of research with its high activity, as US4547600,The patents such as CN1090997, US6717022, US7288686, CN200910236667.0. Although Pd urgesAgent selectively had a larger progress, but still have larger distance compared with the Cu catalyst of KLP. ?In the situation that butadiene price is very high now, the loss that on Pd catalyst, butadiene is larger is unacceptable.
Summary of the invention
The inventor finds by a large amount of experimental studies, the uniformity of Cu catalyst surface element formation alloyAnd dispersed to selecting hydrogenation most important, dispersed relevant with the grain size of main active component, crystal grain is moreLittle dispersiveness is better; Whether uniformity refers to main active component and helps active element to be mixed to get even, uniformityGood main active component is with to help active component to contact more abundant, is more conducive to optionally to improve, catalystLong-term operation. Novel C u catalyst prepared by the present invention, its active component and auxiliary agent can form uniform alloyAnd have polymolecularity, this prepares selective and more traditional infusion process of the one way cycle of operation of catalystCatalyst is greatly improved.
The object of this invention is to provide a kind of copper catalyst that mixes carbon four and select hydrogenation, taking aluminium oxide as carryingBody, and comprise following component (content is the weight percentage taking total catalyst weight as 100%):
(1) active component Cu, 5～50%, be preferably 8～20%;
(2) one or more in auxiliary agent A g, Co, Fe, Mn, Ni, Zn, Cr, Pd, its total contentBe 0.1～20%, be preferably 1～10%;
It is characterized in that the H of described catalyst2-TPR test, wherein H2The peak position of reduction peak exists160～240 DEG C, preferably at 180～220 DEG C, preferably H2The integral area of the main peak of reduction peak accounts for total reduction peak70%～100% of integral area, preferredly accounts for 90%～100%.
In catalyst of the present invention, also can comprise K or Na, its content is 0.05～2%. The ratio table of catalystArea is 40～300m2/ g, pore volume is 0.2～1.2mL/g; Being shaped as of carrier is spherical, bar shaped, tooth are spherical,Cloverleaf pattern or honeycombed; The crystal formation of aluminium oxide is α, θ, δ, γ or mixes crystal formation.
The preparation method who the present invention further provides above-mentioned Cu catalyst, its step is as follows:
(1) first solubility organic amine and water are made into mixed solution, then the soluble-salt of lytic activity component and helpingThe soluble-salt of agent, makes maceration extract, the molal quantity of wherein said solubility organic amine be active component and0.5～5 times of auxiliary agent total mole number, the amount of water equals the water suction of alumina catalyst support to control the amount of final maceration extractAmount is as the criterion;
(2) maceration extract step (1) being prepared is sprayed on alumina support, then leaves standstill aging 5～20h,Dry 5～20h for 60～120 DEG C, after 300～600 DEG C of calcining 2～10h, make finished catalyst.
The soluble-salt of wherein said active component is: in copper nitrate, copper chloride, copper sulphate and copper acetateOne or more; The soluble-salt of auxiliary agent is nitrate, chloride or the acetate of auxiliary agent; Solubility is organicAmine be ethylenediamine tetra-acetic acid, triethanolamine, diethanol amine, monoethanolamine, ethylenediamine, butylamine, diethylamine,Triethylamine, isopropylamine, aniline, DMA, hexamethylene diamine, lauryl amine, triethylene diamine, ringIn hexylamine and hexamethylenetetramine one or more. Preferred solubility organic amine be triethanolamine, monoethanolamine,One or more in ethylenediamine and hexamethylene diamine.
Catalyst of the present invention needs Cu to be reduced to metallic forms before use, can use H2At 250 DEG C, go backFormer 2～10h.
Brief description of the drawings
Fig. 1 is the H of embodiment A catalyst and comparative example A-1 catalyst2-TPR test result. Can in figureTo find out, embodiment A catalyst only has a H2Consume peak, 208 DEG C of left and right, and the catalysis of comparative exampleAgent has two H2Consume peak, respectively at 224 and 259 DEG C. Comparative example catalyst occurs that the reason at two peaks is,Metallic element forms inhomogeneous alloy, and dispersed poor. The H of embodiment catalyst2Consume peak far belowComparative example catalyst, and only have a peak, illustrate Cu and auxiliary element formation alloy more evenly and disperseProperty is better.
Detailed description of the invention
Following examples are to more detailed the describing for example of catalyst of the present invention, but the present invention does not limit toIn these embodiment.
Method of testing:
H2The method of testing of-TPR: the instrument of use is the Autosorb-1-C-TCD of Quantachrome companyChemical adsorption instrument, test process is: take 0.3g sample bead, pack in sample U-shaped pipe, use10％H2-90%Ar (percent by volume) gaseous mixture room temperature blowing down is swept sample cell 10min, temperature programming to 400 DEG C,Heating rate is 10 DEG C/min, uses TCD detector to detect consumption hydrogen peak, TCD bridge electric current 140mA.
Embodiment 1
Take respectively the Cu (NO of 38g3)2·3H2The AgNO of O, 0.79g3Co (NO with 9.9g3)2·6H2O，Measure butylamine 38.2mL, the ratio that makes butylamine and Cu, Ag, Co total mole number is 2: 1, by butylamine and30mL water mixes, then by Cu (NO3)2·3H2O、AgNO3And Co (NO3)2·6H2O adds fourth togetherThe aqueous solution of amine is uniformly dissolved, and is made into maceration extract.
Take 87.5gAl2O3Tooth ball carrier, its specific surface is 197m2/ g, pore volume is 0.6mL/g. Soak above-mentionedStain liquid is sprayed at Al2O3On carrier, then, through leaving standstill aging 5h, dry 10h for 120 DEG C, calcining at 400 DEG C4h, finally makes catalyst A. In catalyst A, Cu content is 10wt%, and Ag content is 0.5wt%, CoContent is 2wt%.
Comparative example 1
Take respectively the Cu (NO of 38g3)2·3H2The AgNO of O, 0.79g3Co (NO with 9.9g3)2·6H2O，It is dissolved in 70mL water together, stirs, make maceration extract.
Take 87.5gAl2O3Tooth ball carrier, its specific surface is 197m2/ g, pore volume is 0.6mL/g, soaks above-mentionedStain liquid is sprayed at Al2O3On carrier, then, through leaving standstill aging 5h, dry 10h for 120 DEG C, calcining at 400 DEG C4h, finally makes catalyst A-1. The element composition of A-1 is identical with catalyst A.
Embodiment 2
Take respectively the Cu (NO of 38g3)2·3H2Ni (the NO of O, 9.9g3)2·6H2Mn (the NO of O, 4.6g50%3)2Solution, 3.8gCr (NO3)3·9H2The AgNO of O, 0.32g3Co (NO with 4.9g3)2·6H2O. Measure twoMonoethanolamine 21.9mL, makes the ratio of the total mole number of diethanol amine and Cu, Ni, Mn, Cr, Ag, CoBe 1: 1, after diethanol amine and 35mL water are mixed, then by Cu (NO3)2·3H2O、Ni(NO3)2·6H2O、Mn(NO3)2、Cr(NO3)3·9H2O、AgNO3、Co(NO3)2·6H2O is dissolved in the aqueous solution of diethanol amine,Be made into maceration extract.
Take 85.8gAl2O3Bead carrier, its specific surface is 115m2/ g, pore volume is 0.5mL/g. Soak above-mentionedStain liquid is sprayed at Al2O3On carrier, then, through leaving standstill aging 5h, dry 10h for 120 DEG C, calcining at 400 DEG C4h, finally makes catalyst B. In catalyst B, Cu content is 10wt%, and Ni content is 2wt%, MnContent is 0.5wt%, and Cr content is 0.5wt%, and Ag content is 0.2wt%, Co content be 1wt% (all withCatalyst gross weight is 100%).
Comparative example 2
Take respectively the Cu (NO of 38g3)2·3H2Ni (the NO of O, 9.9g3)2·6H2Mn (the NO of O, 4.6g50%3)2Solution, 3.8gCr (NO3)3·9H2The AgNO of O, 0.32g3Co (NO with 4.9g3)2·6H2O. By oneRise and be dissolved in 60mL water, stir, be made into maceration extract.
Take 85.8gAl2O3Bead carrier, its specific surface is 115m2/ g, pore volume is 0.5mL/g. Soak above-mentionedStain liquid is sprayed at Al2O3On carrier, then, through leaving standstill aging 5h, dry 10h for 120 DEG C, calcining at 400 DEG C4h, finally makes catalyst B-1. The element composition of B-1 is identical with catalyst B.
Embodiment 3
The present embodiment is evaluated catalyst of the present invention, and test condition is as follows:
Catalyst test carries out in fixed bed reactors, and loaded catalyst is 200mL, before reaction, must useNitrogen replacement, at 250 DEG C, use hydrogen reducing 4h again, mix carbon four raw materials compositions and lists in table 1, mix carbon fourAfter joining hydrogen, from bottom to top flow through reactor, beds inlet temperature is 30～60 DEG C, and reaction pressure is1.0MPa, the liquid air speed of C-4-fraction is 4h-1, the mol ratio (being often called for short hydrogen alkynes ratio) of hydrogen and alkynes is2～4。
The computational methods of reaction residue alkynes and butadiene loss
1. the calculating of the total alkynes of residue:
Remain total alkynes=reaction residue VA+ reaction residue EA+ reaction residue MA
2. the calculating of butadiene loss:
Butadiene content wt% after butadiene content wt%-reaction before butadiene loss wt%=reaction
Table 1 mixes carbon four raw material compositions
| Component | Content (wt%) |
| i-C40 | 2.35 |
| n-C40 | 4.73 |
| tC4＝-2 | 4.49 |
| C4＝1 | 13.90 |
| i-C4＝-1 | 21.31 |
| c-C4＝-2 | 3.36 |
| 1，2-BD | 0.17 |
| 1，3BD | 48.56 |
| MA | 0.08 |
| VA | 0.73 |
| EA | 0.14 |
The evaluation result of catalyst of the present invention is in table 2.
The reaction evaluating result of table 2 catalyst
Can find out from the data of table 2, in the reaction result of comparative example A-1 or B-1, remain alkynes amount and fourthDiene loss amount is all greater than embodiment A or B, illustrates that embodiment's is selectively better than comparative example. Comparative example A-1Just significantly raise in the surplus alkynes amount after 500h of having moved, illustrate that catalyst has now started inactivation, and embodiment existsObvious inactivation just when 1000h; B-1 starts inactivation in the time of 500h, and after B catalyst operation 2000hStill stable in properties. The one way cycle of operation that embodiment catalyst is described is much better than comparative example, demonstrates this speciallyThe huge advantage of profit catalyst.
Claims (13)
1. mix carbon four and select a copper catalyst for hydrogenation, taking aluminium oxide as carrier, and comprise following component,Wherein content is the weight percentage taking total catalyst weight as 100%:
(1) active component Cu, 5～50%;
(2) auxiliary agent A g, its total content is 0.1～20%;
It is characterized in that the H of described catalyst2-TPR test, wherein H2The peak position of reduction peak exists180～220℃。
2. catalyst according to claim 1, is characterized in that: described active component Cu, it containsAmount is 8～20%.
3. catalyst according to claim 1, is characterized in that: described auxiliary agent A g, its content is1～10％。
4. catalyst according to claim 1, is characterized in that: described catalyst also comprise K orNa, its content is 0.05～2%.
5. catalyst according to claim 1, is characterized in that: being shaped as of carrier is spherical, bar shaped,Tooth is spherical, cloverleaf pattern or honeycombed.
6. catalyst according to claim 1, is characterized in that: the crystal formation of aluminium oxide be α, θ, δ,γ or mixing crystal formation.
7. catalyst as claimed in claim 1, is characterized in that: the H of described catalyst2-TPR test,Wherein H2The integral area of the main peak of reduction peak accounts for 70%～100% of total reduction peak integral area.
8. catalyst as claimed in claim 7, is characterized in that: the H of described catalyst2-TPR test,Wherein H2The integral area of the main peak of reduction peak accounts for 90%～100% of total reduction peak integral area.
9. the method for the catalyst described in one of preparation claim 1～8, is characterized in that described preparation sideMethod comprises the following steps:
(1) first solubility organic amine and water are made into mixed solution, then the soluble-salt of lytic activity component and helpingThe soluble-salt of agent, makes maceration extract, the molal quantity of wherein said solubility organic amine be active component and0.5～5 times of auxiliary agent total mole number, the amount of water equals the water suction of alumina catalyst support to control the amount of final maceration extractAmount is as the criterion;
(2) maceration extract step (1) being prepared is sprayed on alumina support, then leaves standstill aging 5～20h,Dry 5～20h for 60～120 DEG C, after 300～600 DEG C of calcining 2～10h, make finished catalyst.
10. preparation method according to claim 9, is characterized in that, the soluble-salt of active component isOne or more in copper nitrate, copper chloride, copper sulphate and copper acetate.
11. preparation methods according to claim 9, is characterized in that, the soluble-salt of auxiliary agent is auxiliary agentNitrate.
12. preparation methods as claimed in claim 9, is characterized in that, solubility organic amine is ethylenediamine tetraaceticAcetic acid, triethanolamine, diethanol amine, monoethanolamine, ethylenediamine, butylamine, diethylamine, triethylamine, isopropylAmine, aniline, DMA, hexamethylene diamine, lauryl amine, triethylene diamine, cyclohexylamine and six firstOne or more in urotropine.
13. preparation methods as claimed in claim 12, is characterized in that, solubility organic amine is three ethanolOne or more in amine, monoethanolamine, ethylenediamine and hexamethylene diamine.
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