CN1028841C - Paraffin hydro-isomerized super strong acid catalyzer - Google Patents
Paraffin hydro-isomerized super strong acid catalyzer Download PDFInfo
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- CN1028841C CN1028841C CN 92101682 CN92101682A CN1028841C CN 1028841 C CN1028841 C CN 1028841C CN 92101682 CN92101682 CN 92101682 CN 92101682 A CN92101682 A CN 92101682A CN 1028841 C CN1028841 C CN 1028841C
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Abstract
The present invention relates to a super strong acid catalyst for paraffin hydro-isomerization, which is composed of manganese oxide or manganese hydroxide, iron oxide or iron hydroxide, 0.1 to 2.0 wt% of Pt and Pd, 2.0 to 16.0 wt% of SO4<2-> and an equilibrium amount of zirconium oxide or zirconium hydroxide, wherein the manganese content is from 0.1 to 1.0 wt%, and the iron content is from 0.5 to 2.0 wt%. The catalyst is used for the isomerization reaction of C4 to C10 paraffin and is particularly suitable for the isomerization reaction of C5 to C6 paraffin.
Description
The invention relates to a kind of paraffin hydro-isomerized super strong acid catalyzer.Specifically about a kind of Pt or Pd/Zr, Mn, Fe oxide or hydroxide/SO that is used for alkane hydroisomerization
2- 4The system super acidic catalyst.
Super acids is the acid stronger than sulfuric acid, its Ho≤-12, and it is very capable to the carbonium ionization of organic compound, can react by the organifying compound under the condition that relaxes very much, is applicable to the conversion reaction of various hydro carbons.As isomerization, cracking, hydrocracking, dehydration, alkylation and dealkylation reaction etc.
At present, the AlCl of industrial extensive use
3Catalyst can make alkane carry out isomerization reaction under lower temperature, but because of the problems such as processing of its etching apparatus, contaminated environment and catalyst are restricted, though liquid superacid and halogen-containing solid super-strong acid are very strong lewis acid and Bronsted acids, and has a good reaction activity, but because they contain halogen, produce the three wastes in synthetic and processing catalyst process, contaminated environment has limited its application equally.Therefore, the another kind of non-halogen super acids that generally begins one's study now.1979, Hino's one-tenth waits reported SO
2- 4/ MxO
yType super acids (catalyst 4,217,1979), it is with SO
2- 4Be adsorbed on the surface of metal oxide or hydroxide, make through high-temperature roasting, its acid strength is equivalent to 104 times in sulfuric acid; Human H such as Hino
4TiO
4And 1NH
2SO
4Contact has been made the SO that is suitable for alkane isomerization 500 ℃ of roastings then
2- 4/ TiO
2Super acids (J.S.C.Chem.Comm1979,1148); People such as Hino also use 1NH
2SO
4Handle zirconium hydroxide, made SO through high-temperature roasting
2- 4/ ZrO
2Super acids (J.A.m.Chem.Soc.10,1979,6439); They also find to use H
2SO
4Handle Fe
2O
3, after high-temperature roasting, Fe
2O
3The acidity and the catalytic activity all be significantly increased (Chem.Lett.477,1979) on surface; MatsuhashI.H. wait the people to develop SO
2- 4/ SnO
2Super acids (Chem.Lett.1027,1988); EP0,365,147A has reported with the oxide of III A, IV B family metal or hydroxide and V B, VI B, the oxide of VII B family metal or the oxide or the hydroxide immersion SO of hydroxide and group VIII metal
2- 4The super acidic catalyst of making after roasting is used for C
4-C
7N-C has been put down in writing in the alkane isomerization reaction in the example
4When carrying out isomerization reaction for 100 ℃, the isomerized products yield can reach 24.58 heavy %, carries out isomerization reaction at 75 ℃, and yield reaches 55.08 heavy %, but this catalyst is used for n-C
6When carrying out isomerization reaction for 130-150 ℃, isomerized products is almost nil, and reactor product is all cracking almost, cause catalyst carbon deposit, inactivation.
The objective of the invention is to improve on the basis of existing technology, prepare a kind of C that is applicable to
4-C
10The alkane isomerization reaction is specially adapted to C
5-C
6Paraffin hydro-isomerized super strong acid catalyzer makes it to have higher isomerization reaction activity and selectivity.
Catalyst provided by the invention, it consists of: oxide or the hydroxide of (1) Mn, wherein Mn content is the heavy % of 0.1-1.0; (2) oxide of Fe or hydroxide, wherein Fe content is the heavy % of 0.5-2.0; (3) the heavy % of precious metals pt or Pd0.1-2.0; (4) SO
2- 42.0-16.0 heavy %; (5) the Zr oxide or the hydroxide of aequum.Its preparation process is as follows:
1, Zr, Mn, Fe salt are dissolved in the deionized water, making salt-mixture concentration is the aqueous solution of the heavy % of 4.0-5.0, and wherein the Mn salinity is the heavy % of 0.01-0.20, and the Fe salinity is the heavy % of 0.1-0.5.
2, under agitation ammoniacal liquor and above-mentioned mixing salt solution are added drop-wise in the deionized water simultaneously, control pH is 3.5-10, and preferably 7-10 generates precipitation of hydroxide, after precipitation is complete, pH is transferred to neutrality, filters, precipitation is washed till no acid group, in 100-200 ℃ of drying 24 hours, porphyrize＜150 orders.
3, soak noble metal with saturated infusion process, to make in the catalyst bullion content be the heavy % of 0.1-2.0, at 120-300 ℃, preferably 200 ℃ of oven dry.
4, soak with saturated infusion process and contain SO
2- 40.73-21.82 heavy %, the preferably H of the heavy % of 8.0-16.0
2SO
4Or (NH
4)
2SO
4Solution makes SO in the catalyst
2- 4Content is the heavy % of 2.0-16.0, oven dry.
5, in 550-750 ℃ of roasting 0.5-5 hour.
6, reduced 0.5-4 hour under nitrogen atmosphere in 200-350 ℃, preferably 250-300 ℃ of reduction 1-2 hour.
The said catalyst of the present invention is in the preparation method, and Zr salt is ZrOCl
2, ZrO(NO
3)
2, Zr(NO
3)
4; Mn salt is meant MnCl
2, Mn(NO
3)
2, Fe salt is meant FeCl
3, Fe(NO
3)
3; The noble metal precursor is H
2PtCl
6Solution or with PdCl
2Be dissolved in the H that makes in the hydrochloric acid
2PdCl
4Solution.
Said Zr can replace with other metal of IV B family among the present invention, as Ti, and Hf, Mn can replace Tc, Re with other metal of VII B family.
Adopt Pt or Pd/Zr, Mn, Fe oxide or the hydroxide/SO of the present invention's preparation
2- 4The system super acidic catalyst is applicable to C
4-C
10The isomerization of paraffinic hydrocarbons reaction.To n-C
6Isomerization reaction not only has high activity, and has good selectivity.As at 130-150 ℃ to n-C
6When carrying out isomerization reaction, yield reaches the heavy % of 63.8-89.9,2, the 2-dimethylbutane in the time of 150 ℃ selectivity up to 34.5%.In addition, 2, the concentration of 2-dimethylbutane in product is formed is suitable with thermodynamical equilibrium numerical value.
The following examples are described further the present invention.
Example 1
With 36.1 gram MnCl
24H
2The O(Beijing Chemical Plant analyzes pure) be dissolved in and make 500 ml solns in the deionized water, with 144.8 gram FeCl
36H
2Chemical plant, the 17 middle school, O(Beijing is analyzed pure) be dissolved in and make 500 ml solns in the deionized water, take out 4 milliliters of MnCl then
2Solution and 4 milliliters of FeCl
3Solution and 38.2 gram ZrOCl
28H
2The O Beijing Chemical Plant analyzes pure) be dissolved in and make 500 ml soln first in the deionized water.Measure 20.0 milliliters of concentrated ammonia liquors and make 300 ml soln second with the deionized water dilution.Also under agitation solution first and solution second slowly are added drop-wise in the flask that fills 500 ml deionized water simultaneously in room temperature, control pH=7 generates precipitation of hydroxide, filtering-depositing, be washed till no acid group, then about 24 hours of 120 ℃ of dryings, with sample porphyrize＜150 orders of above-mentioned oven dry.Take by weighing the above-mentioned sample of 6.0 grams, be impregnated into 3.0 milliliters of H that contain the heavy % of Pd1.0
2PdCl
4(H in the solution
2PdCl
4Solution is with PdCl
2Be dissolved in and make in the hydrochloric acid, down with), in 200 ℃ of oven dry, immerse 3.0 milliliters then and contain SO
2- 48.0 (the NH of heavy %
4)
2SO
4Solution, the oven dry, 600 ℃ of roastings 2 hours, then under nitrogen atmosphere in 250 ℃ the reduction 1 hour, promptly get catalyst A.
Example 2
The preparation method just soaks 6.0 milliliters of H that contain the heavy % of Pd1.0 with example 1
2PdCl
4Solution and 3.0 milliliters contain SO
2- 416.0 (the NH of heavy %
4)
2SO
4Solution, the gained catalyst B.
Example 3
The preparation method is with example 2, and the pH value controls to 4-5 when being precipitation of hydroxide, transfers to neutrality with ammoniacal liquor again after precipitation is complete, and the gained catalyst is C.
Example 4
The preparation method is with example 2, and when being precipitation of hydroxide, the pH value is controlled to be 10, and post precipitation is transferred to neutrality with watery hydrochloric acid again, and the gained catalyst is D.
Comparative example 1
Preparation of Catalyst does not just contain Pd with example 1, makes catalyst E.
Example 5
The super acidic catalyst of estimating the present invention's preparation is to n-C
6Isomerization reaction activity.
On normal pressure pulse micro-inverse device, with n-C
6Be raw material, the activity of the super acidic catalyst of evaluation example 1-4 and comparative example 1 preparation.80-100 order loaded catalyst is 0.2 milliliter, H
2Throughput is 50 ml/min, 200 ℃ of reaction temperatures, n-C
6Sample size is 1.0 microlitres, the results are shown in Table 1, as can be seen from Table 1, with catalyst provided by the invention at 200 ℃ of same n-C
6Carry out isomerization reaction, when PH was 7-10, yield reached the heavy % of 63.0-78.8, when pH is 4-5, though yield has only 31.4 heavy %, but the selectivity of its isomeric alkane reaches 100%, and according to the catalyst E that prior art prepares, carries out isomerization reaction under similarity condition, though conversion ratio can reach 93.6 heavy %, but its isomerized products yield has only 6.8 heavy %, and the overwhelming majority is a pyrolysis product, reaches 86.8 heavy %.
After table 1 is seen literary composition
Example 6-10
The preparation method is with example 2, the SO that just is written into
2- 4Different with Pd content, wherein immerse the H that contains Pd
2PdCl
4Solution and contain SO
2- 4(NH
4)
2SO
4Solution is respectively:
After table is seen literary composition
Example 11
The preparation method is with example 2, and just immersion contains the heavy %H of Pt1.0
2PtCl
63.0 milliliters of solution contain SO
2- 416.0 (the NH of heavy %
4)
2SO
43.0 milliliters of solution make catalyst K.
Comparative Examples 2
The preparation method does not just contain Pd with example 2, makes catalyst L.
Example 12
With the catalyst of example 6-11 and Comparative Examples 2 preparations on the continuous micro-reactor of pressurization with n-C
6For raw material carries out activity rating, reaction condition is as follows: fixed bed, and 0.75 milliliter of 80-100 order catalyst loading amount, the liquid volume air speed is 4 o'clock
-1, H
2/ n-C
6Mol ratio=5.0, pressure 10 kilograms per centimeter
2, reaction temperature 130-150 ℃, reaction is carried out later the results are shown in Table 2 in 1 hour.
As can be seen from Table 2, with the catalyst of the present invention preparation to n-C
6Carry out isomerization reaction at 130-150 ℃, yield reaches the heavy % of 63.8-89.9, and react under similarity condition according to the catalyst L of prior art preparation, the product that obtains almost all is a pyrolysis product, and owing to the serious carbon deposit of catalyst causes catalysqt deactivation.
Table 3 has been enumerated n-C
6When carrying out isomerization reaction, the comparison of the yield of 2.2-dimethylbutane and thermodynamical equilibrium numerical value.As can be seen from Table 3, adopt the n-C of the catalyst of the present invention's preparation
6Carry out isomerization reaction at 150 ℃, the concentration of 2.2-dimethylbutane in product is formed is suitable with its thermodynamical equilibrium numerical value.
After table 2 is seen literary composition
Example 13
The preparation method is with example 2, and just immersion contains SO
2- 416.0 (the NH of heavy %
4)
2SO
44.0 milliliters of solution make catalyst M.
Example 14
With the catalyst of example 13 preparation on the continuous micro-reactor of pressurization to n-C
5Estimate, reaction condition is as follows: fixed bed, 2.0 milliliters of 80-100 order catalyst-assemblies, volume space velocity are 1.5 o'clock
-1, n-C
5/ H
2Mol ratio=1.5, pressure 10 kilograms per centimeter
2, 140 ℃ of reaction temperatures are reacted and later be the results are shown in Table 4 in 1.5 hours.
As can be seen from Table 4, the prepared catalyst of the present invention is to n-C
5Isomerization reaction also has higher activity.
After table 4 is seen literary composition
Table 1
Urge hydroxide conversion ratio product to form (mole %)
Catalyst is formed (heavy %) (mole %) when changing precipitation
Agent pH value isomerized products pyrolysis product n-alkane
A 7 1.5Fe，0.5Mn，0.5Pd，4.0SO
2- 4/ZrO
284.0 78.8 5.2 16.0
B 7 1.5Fe，0.5Mn，1.0Pd，8.0SO
2- 4/ZrO
268.0 66.9 1.1 32.0
C 4-5 1.5Fe，0.5Mn，1.0Pd，8.0SO
2- 4/ZrO
231.4 31.4 0 68.6
D 10 1.5Fe，0.5Mn，1.0Pd，8.0SO
2- 4/ZrO
263.0 63.0 0 37.0
E 7 1.5Fe，0.5Mn，4.0SO
2- 4/ZrO
293.6 6.8 86.8 6.4
Annotate: (1) isomerization product refers in the table: 2.2-dimethylbutane (2.2DMB);
2.3-dimethylbutane (2.3DMB);
2-methylpentane (2MP);
3-methylpentane (3MP).
(2) pyrolysis product refers to C
5Following alkane.
(3) n-alkane refers to n-C
6Raw material.
Down together.
H is urged in experiment
2PdCl
4Solution (NH
4)
2SO
4Solution
Numberingization Pd content (heavy %) milliliter number SO
2- 4Content (heavy %) milliliter number
Agent
6 F 1.0 1.5 16.0 3.0
7 G 1.0 3.0 16.0 3.0
8 H 1.0 6.0 16.0 3.0
9 I 1.0 9.0 16.0 3.0
10 J 1.0 12.0 16.0 3.0
Table 2
Urge the reaction conversion ratio product to form (mole %)
Change catalyst and form (heavy %) temperature (mole %)
Agent (℃) isomerized products pyrolysis product n-alkane
F 1.5Fe，0.5Mn，0.25Pd，8.0SO
2- 4/ZrO
2130 70.9 70.9 0 29.1
G 1.5Fe，0.5Mn，0.5Pd，8.0SO
2- 4/ZrO
2150 82.0 82.0 0 18.0
H 1.5Fe，0.5Mn，1.0Pd，8.0SO
2- 4/ZrO
2150 90.4 89.9 0.5 9.6
H 1.5Fe，0.5Mn，1.0Pd，8.0SO
2- 4/ZrO
2130 87.0 87.0 0 13.0
I 1.5Fe，0.5Mn，1.5Pd，8.0SO
2- 4/ZrO
2130 83.1 83.1 0 16.9
J 1.5Fe，0.5Mn，2.0Pd，8.0SO
2- 4/ZrO
2130 63.8 63.8 0 36.2
K 1.5Fe，0.5Mn，0.5Pt，8.0SO
2- 4/ZrO
2150 80.8 80.8 0 19.2
L 1.5Fe，0.5Mn，8.0SO
2- 4/ZrO
2150
Almost all be pyrolysis product and cause the catalyst carbon deposit inactivation.
Table 3
Urge the anti-2.2-dimethylbutane of isomerization yield (mole %)
Changing the catalyst composition answers temperature to adopt the catalyst thermodynamical equilibrium
Agent (heavy %) (℃) the yield measured value * of H
H 1.5Fe，0.5Mn，1.0Pd8.0SO
2- 4/ZrO
2150℃ 31.0 30.5
* annotate: select from " Huadong Chemical College journal " 13(2), 209(1989)
Thermodynamical equilibrium pH-value determination pH temperature: 150 ℃
Table 4
Urge the conversion ratio product to form (mole %)
Change catalyst and form (heavy %) (mole %) positive structure of isocracking
Agent product product alkane
M 1.5Fe，0.5Mn，1.0Pd，10.7SO
2- 4/ZrO
278.3 76.4 1.9 21.7
Claims (10)
1, a kind of Zr, Mn, Fe oxide or hydroxide/SO of containing
2- 4Paraffin hydro-isomerized super strong acid catalyzer, it is characterized in that it has following composition:
(1) oxide of Mn or hydroxide, wherein Mn content is the heavy % of 0.1-1.0;
(2) oxide of Fe or hydroxide, wherein Fe content is the heavy % of 0.5-2.0;
(3) precious metals pt or the Pd of the heavy % of 0.1-2.0;
(4) SO of the heavy % of 2.0-16.0
2- 4
(5) oxide of the Zr of aequum or hydroxide.
2,, it is characterized in that this Preparation of catalysts method is according to the said catalyst of claim 1:
(1) Zr, Mn, Fe salt are dissolved in the deionized water, the concentration of making salt-mixture is the aqueous solution of the heavy % of 4.0-5.0, and wherein the Mn salinity is the heavy % of 0.01-0.20, and the Fe salinity is the heavy % of 0.1-0.5;
(2) under agitation, ammoniacal liquor and above-mentioned mixing salt solution are added drop-wise in the deionized water simultaneously, control pH is 3.5-10, generate precipitation of hydroxide, after precipitation is complete pH is transferred to neutrality, filter, precipitation is washed till no acid group, in 100-200 ℃ of drying 24 hours, porphyrize＜150 orders;
(3) soak noble metal, making in the catalyst bullion content is the heavy % of 0.1-2.0, in 120-300 ℃ of drying;
(4) soak SO
2- 4, make SO in the catalyst
2- 4Content is the heavy % of 2.0-16.0, drying;
(5), under nitrogen atmosphere, reduced 0.5-4 hour at 200-350 ℃ in 550-750 ℃ of roasting 0.5-5 hour.
3, catalyst according to claim 2 is characterized in that said Zr salt is ZrOCl in (1)
2, ZrO(NO
3)
2, Zr(NO
3)
4
4,, it is characterized in that said Mn salt is meant MnCl2, Mn(NO in (1) according to the said catalyst of claim 2
3)
2
5,, it is characterized in that said Fe salt is meant FeCl in (1) according to the said catalyst of claim 2
3, Fe(NO
3)
3
6,, it is characterized in that said pH value controls to 7-10 in (2) according to the said catalyst of claim 2.
7,, it is characterized in that said adjusting pH value is meant with watery hydrochloric acid or rare nitric acid or ammoniacal liquor adjusting pH value to neutrality in (2) according to the said catalyst of claim 2.
8, according to the said catalyst of claim 2, the precursor that it is characterized in that said noble metal in (3) is H
2PtCl
6Solution or with PdCl
2Be dissolved in the H that makes in the hydrochloric acid
2PdCl
4Solution.
9,, it is characterized in that said SO in (4) according to the said catalyst of claim 2
2- 4Precursor be H
2SO
4Or (NH
4)
2SO
4Solution.
10, according to the said catalyst of claim 9, it is characterized in that said H
2SO
4Or (NH
4)
2SO
4In the solution, SO
2- 4Content is the heavy % of 0.73-21.82.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92101682 CN1028841C (en) | 1992-03-23 | 1992-03-23 | Paraffin hydro-isomerized super strong acid catalyzer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92101682 CN1028841C (en) | 1992-03-23 | 1992-03-23 | Paraffin hydro-isomerized super strong acid catalyzer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1076639A CN1076639A (en) | 1993-09-29 |
| CN1028841C true CN1028841C (en) | 1995-06-14 |
Family
ID=4939242
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92101682 Expired - Fee Related CN1028841C (en) | 1992-03-23 | 1992-03-23 | Paraffin hydro-isomerized super strong acid catalyzer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1028841C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1914216A4 (en) * | 2006-06-19 | 2017-11-01 | Limited Liability Company "Scientific Industrial Enterprise Neftehim" | Method for isomerising light gasoline fractions |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5494569A (en) * | 1994-01-21 | 1996-02-27 | Sun Company, Inc. (R&M) | Hydrocracking using solid superacid catalysts comprising platinum metal |
| US5516964A (en) * | 1994-01-21 | 1996-05-14 | Sun Company, Inc. (R&M) | Hydrocarbon isomerization using solid superacid catalysts comprising platinum metal |
| US5494571A (en) * | 1994-01-21 | 1996-02-27 | Sun Company, Inc. (R&M) | Naphtha upgrading using solid superacid catalysts comprising platinum metal |
| CA2254129A1 (en) * | 1998-11-13 | 2000-05-13 | Uop | Selective, rugged layered isomerization catalyst for use in a paraffin isomerization process |
| CN103059912B (en) * | 2011-10-18 | 2015-02-25 | 中国石油化工股份有限公司 | Isomerization reaction method of straight-chain paraffin |
| CN103059911B (en) * | 2011-10-18 | 2015-03-18 | 中国石油化工股份有限公司 | Isomerization reaction method of straight-chain paraffin |
-
1992
- 1992-03-23 CN CN 92101682 patent/CN1028841C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1914216A4 (en) * | 2006-06-19 | 2017-11-01 | Limited Liability Company "Scientific Industrial Enterprise Neftehim" | Method for isomerising light gasoline fractions |
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| Publication number | Publication date |
|---|---|
| CN1076639A (en) | 1993-09-29 |
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Granted publication date: 19950614 Termination date: 20100323 |