CN1021114C - Phosphoric acid/active carbon catalyst and coincidence process - Google Patents
Phosphoric acid/active carbon catalyst and coincidence process Download PDFInfo
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- CN1021114C CN1021114C CN 90107695 CN90107695A CN1021114C CN 1021114 C CN1021114 C CN 1021114C CN 90107695 CN90107695 CN 90107695 CN 90107695 A CN90107695 A CN 90107695A CN 1021114 C CN1021114 C CN 1021114C
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- low temperature
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Abstract
The present invention relates to a phosphoric acid and active carbon catalyst for preparing high-octane petrol by mixing alkene or C4 alkene. The technology has the advantages of high activity, good selectivity, high oil production rate, simple processes of catalyst preparation and polyreaction, etc., and has the specific indexes: 1, 130 DEG C to 230 DEG C of reaction temperature, LHSV2.5 to 5.0 hr+[1] of the space velocity of reaction raw material, and 2.0 M pa to 6.0 M pa of reaction pressure; 2, 0.56kg catalyst / ton gasoline to 0.72kg catalyst / ton gasoline of unit consumption of catalyst; 3, the octane value RON of petroleum product is from 9 to 99, and MON is from 82 to 85; a dry point of heat bodied oil is lower than 196 DEG C.
Description
The present invention relates to a kind of low temperature coincidence process and belong to the refining of petroleum field, specially refer to and utilize the activated carbon of phosphoric acid catalyzer to make alkene oligomerization produce stop bracket gasoline technology.
Well-known domestic and international non-selective coincidence process still uses UOP technology, its solid phosphoric acid polymerization catalyst is carrier with diatomite, diatomite and phosphatizing generate phosphoric acid silicon in preparation process, and phosphoric acid is adsorbed on the carrier surface more securely, thereby think that this phosphoric acid is nonvolatile, there is acid to be difficult for the advantage that runs off, so catalyst stream reaches the present, and this catalyzer disadvantage to be phosphoric acid silicon can deliquescing under the steam effect reduce its physical strength, UOP phosphoric acid catalyst SPA-1 unit consumption is 1.4-1.6Kg catalyzer/t gasoline under the normal circumstances, and the similar catalyst unit consumption that Jinzhou Liu Chang and Nan Zhao produce competes to reach 5-8Kg catalyzer/t gasoline, this be since before the catalyst deactivation because of due to argillization increases the reactor resistance to be forced to stop work.Germany once used the activated carbon of phosphoric acid catalyzer at Co+H during the World War II
2The lamination process of gas in the synthetic gasoline, Pd/carbon catalyst great advantage are that intensity is good, argillization not, but owing to phosphoric acid sorption property difference being easy to run off reaction raw materials air speed 0.8h under 30atm
-1Time oil yield is 480Kg gasoline/Kg catalyzer, and the corresponding catalyst unit consumption is 2.1Kg catalyzer/t gasoline.The seventies petroleum science research institute of reviving has entirely developed a kind of " two skeleton " synthetic carrier AY, its preparation process is earlier with water glass dipping carrier gac, and then neutralize with sulfuric acid, silica gel is among the gac skeleton, thereby it has the advantage of diatomite and two kinds of carriers of gac, promptly physical strength is good, argillization not, and the advantage that acid is not run off has reached good effect, but does not carry out suitability for industrialized production because preparation process is too complicated.
The purpose of this invention is to provide a kind of low temperature coincidence process that uses novel activated carbon of phosphoric acid.The present invention provides a kind of low temperature coincidence process employed activated carbon of phosphoric acid Catalysts and its preparation method simultaneously.
The present invention comprises for used the activated carbon of phosphoric acid catalyzer in low temperature coincidence process process: (a) in reactor, helping under the superimposed operational condition, the liquefied gas raw material is contacted with polymerization catalyst, thereby obtain product liquid and gaseous stream, said polymerization catalyst is H
3PO
4/ activated-carbon catalyst (b) is isolated the aforesaid liquid product from above-mentioned gaseous stream, (c) above-mentioned product liquid C
5-C
9Branched-chain alkene, promptly polymer gasoline (d) is recycled to above-mentioned gas stream in the above-mentioned reactor.Low temperature coincidence process process, wherein said gas stream comprise positive isoparaffin and the various alkene of not participating in building-up reactions of not participating in building-up reactions.Wherein said separating step (b) comprises flash distillation and stable.Helping superimposed operational condition is: reaction pressure 2.0-6.0MPa, and 130 ℃-230 ℃ of temperature of reaction, the liquid air speed is 2.5-5.0h
-1The product liquid that reaction is generated accounts for more than 40% of reactor feed gross weight.The H that is used for the low temperature coincidence process
3PO
4/ activated-carbon catalyst is to be carrier dipping technical pure H with gac
3PO
4Form, wherein gac is a coal mass active carbon, and the specific surface area of coal mass active carbon is 700～1300M
3/ g, pore volume 0.4～0.8ml/g, bulk density 0.3-0.5, coal mass active carbon will give processing with technical hydrochloric acid in advance, and concentration of hydrochloric acid is selected from 1: 1, the technical hydrochloric acid of 1: 4 and 1: 8, and technical pure H
3PO
4Concentration 8: 2(acid: water), H
3PO
4Immersion condition reflux 2-8 hour, H
3PO
4H in the/activated-carbon catalyst
3PO
4Content is 30-60%, H
3PO
4Will give activation before the reaction of/activated-carbon catalyst, giving activation condition is at nitrogen medium 1000-2000h
-1, 2.5mpa, 200-250 ℃, give activation 2～4 hours, perhaps use 1000-1200h under the air dielectric condition
-1, 0-0.5MPa, 200-250 ℃, 2-4 hour.
The carrier of activated carbon of phosphoric acid catalyzer adopts the ature of coal pressed active carbon, and its physical parameter is: bulk density is 0.3-0.5; Specific pore volume is long-pending to be 0.4-0.8ml/g; Specific area is 700-1300m
2/ g.Its chemical constitution contains multiple major element and trace element, is Al16.32 in the relative foreign matter content in atomic percentage conc At% carrier surface; Si46.21; P22.29; K0.97; Ca1.94; Fe12.16.The carrier molten foreign matter content of acid (mg/g) is Al35.83; Fe11.556; Ca4.583; Mg0.7448; Ba0.1569; Be0.2836 * 10
-3; Co6.597 * 10
-3; Cu3.87 * 10
-3; Cr5.595 * 10
-3; Mn1.54 * 10
-1; Ni1.50 * 10
-2; P5.97 * 10
-2; Sr2.66 * 10
-3; Ti3.34 * 10
-2; V1.20 * 10
-2; Y7.40 * 10
-3With above-mentioned carrier in 1: 1～1: 8 hydrochloric acid (volume ratio) reflux 2-8 hour, wash acid-soluble material and residual acid with water, till neutrality, reheat boiling washing extremely no longer shows till the acidity, draining the back becomes the carrier that has made 100-150 ℃ of oven dry constant weight, and its foreign matter content At% is: Al19.53; Si56.13; P16.35; Fe6.83.Its acid-soluble material foreign matter content mg/g is: Al0.5052; Fe0.4817; Ca0.2926; Mg6.06 * 10
-2; Ba4.52 * 10
-1; Co1.20 * 10
-1; Cu5.14 * 10
-3; Mn5.18 * 10
-3; Ni3.60 * 10
-3; P2.813 * 10
-3; Si3.013 * 10
-3; Ti0.146 * 10-3; V2.814 * 10
-3; Y1.01 * 10
-2Because of Si is not dissolved by hydrochloric acid, to improve be because of having removed due to the acid-soluble material to Si content from relative foreign matter content.With the carrier for preparing with 4: 6-9: 1(is with 85%H
3PO
4With the water volume ratio meter), different phosphoric acid concentrations was reduced to about 95 ℃ with equal-volume carrier amount reflux and is drained in conical hopper in 0.5-3 hour, 110-150 ℃ of oven dry constant weight, make activated carbon of phosphoric acid catalyst buildup proportion at 0.7-1.0, its relative phosphorus is 30-60%; Its intensity is 12～17Kg/cm
2
Selecting the higher coal mass active carbon of silicon content for use is carrier, and it contains SiO
2Amount can be at 3-8%, and it is among the gac skeleton, has played the effect of natural " two skeleton " carrier, with the phosphoric acid catalyst of this carrier preparation after activation, the SiO in phosphoric acid and the carrier in reaction process especially
2Confirmed that by the x optical diffraction analysis it generates biphosphate silicon, phosphoric acid hydrogen silicon and phosphoric acid silicon etc., because their existence has improved the performance of activated carbon of phosphoric acid catalyzer, avoid phosphoric acid infusorial earth catalyst argillization and the caked shortcoming of bonding in reaction process again, thereby obtained higher yield of gasoline.At 40atm, under the reaction conditions of 100-140ml catalyst-assembly, resulting oil yield rate is 1355-1790Kg gasoline/Kg catalyzer, and its corresponding unit consumption is 0.56-0.72Kg catalyzer/t gasoline.
Effect of the present invention is to use the activated carbon of phosphoric acid catalyzer to make mixed olefins or C in the low temperature coincidence process
4Alkene oligomerization prepares octane value gasoline, and this catalyzer has active high, and selectivity is good, the oil yield rate height, catalyst consumption hangs down 0.56-0.72Kg catalyzer/t gasoline, the high RON=97-99 of gasoline octane rating, MON=82-85, temperature of reaction 130-230 ℃, reaction raw materials air speed 2.5-5.0hr
-1, reaction pressure 2.0-6.0MPa, catalyst preparation process of the present invention is simple, need not to add acid and mediates and high-temperature roasting.Building-up reactions technology is simple, and the portability minor amount of water can be kept the catalyst surface water partial pressure during unstripped gas washing, has saved outer water filling operation, and under control differential responses temperature condition, the activated carbon of phosphoric acid catalyzer can be applicable to the superimposed and C of the non-selection of hydrocarbon mixture respectively
4Hydrocarbon-selective is superimposed.The catalyst activity height is reflected at 3.0-4.0hr
-1The raw material liq air speed time still can keep the one way liquid yield and be higher than 40%, thereby higher plant factor is arranged.Catalyst selectivity is good, and product oil boiling range does≤and 196 ℃, stable back all is a gasoline fraction.
Accompanying drawing and explanation thereof
Accompanying drawing 1 is a coincidence process schematic flow sheet of using the activated carbon of phosphoric acid catalyzer.
A-washing tower 4-waste liquid
B-tundish 5-waste liquid return wire
C-heat exchanger 6-gives the liquefied gas after the heat
D-is equipped with the reactor 7-polymer gasoline of phosphoric acid/active carbon catalyst
E-flash tank 8-quenching oil
The unreacted boil-off gas of F-chilling oil tank 9-
Polymer gasoline after the G-stabilizer tower 10-flash distillation
H-return tank 11-unreacted liquefied gas
1-NaH
2PO
4Aqueous solution 12-unreacted liquefied gas
2-stock liquid gasification 13-polymer gasoline
The liquefied gas 14-stabilizer tower return wire of 3-after washing
The coal mass active carbon that will contain 6% silicon-dioxide, the moulding granularity is D25mm * 2.5mm, is 1 with it with concentration: 4(acid: technical hydrochloric acid water) carries out pickling, heating 95-105 ℃ refluxed four hours, its objective is that in order to remove sour molten impurity such as de-iron, calcium, magnesium washing is removed acid-soluble material and residual acid till the neutrality then, after draining, oven dry makes carrier, specific surface area 1300m under 115-120 ℃
2/ g, specific pore volume amasss 0.7125ml/g, bulk density 0.45.Get 200 gram carriers, with 1: 1 industrial phosphoric acid dipping, phosphoric acid concentration 8: 2(acid: water), heat 100-110 ℃ backflow 2-4 hour, drain, 110-120 ℃ of oven dry, activate and make H
3PO
4/ activated-carbon catalyst, its bulk density are 0.88, phosphorus acid content 58 gram H
3PO
4/ 100 gram catalyzer, mechanical strength value is 17.00Kg/cm
2
The gac that 200 grams are handled well drains with the phosphoric acid heating dipping of 200ml70%, 14 hours catalyzer of 118 ℃ of bakings, and bulk density is 0.79; Be reflected at diameter 39 * 7mm, carry out in the stainless steel reaction pipe of long 920mm.The catalyzer loading amount is 140ml, heats up 245 ℃ before the reaction, logical N
2Activate 3 hours; Be cooled to 100 ℃ then, and the hydrocarbon mixture of feeding process caustic wash desulfuration (its component is a propylene 28%, propane 9%, and n-butene 6% is along anti-butylene
-214%, iso-butylene 10%, normal butane 8%, Trimethylmethane 19%, alkene 58%), 170～220 ℃ of temperature of reaction, raw material air speed 3.5～4.0hr
-1, reaction pressure 4.0MPa, liquid yield＞40%, continuous operation 55 days, product oil are after gas is caught up with in 40 ℃ of backflows, and the stabilize oil yield is 1355 kilograms of oil/kilogram catalyzer, the oil product water white transparency, proportion 0.6994 is done 193 ℃, C in the oil
7+ C
8=55%, copper corrosion is qualified, and the soda acid test is for neutral, and bromine number 92.72 gram bromines/100 restrain oil, octane value 97.5(RON), 82.4(MON) non-caked with the back spent catalyst, easily unload, degradation rate 10～20 orders are 3.07%,＜20 orders 5.95%, product oil boiling range is:
Fore-running 10% 50% 90% is done
42℃ 67℃ 107℃ 166℃ 193℃
Rate of loss 4%
Total quantity of distillate: 94%
Resid amount: 2%
Preparation activated carbon of phosphoric acid catalyzer, its bulk density D=0.88, use-case 2 reactors, carrier 21.8g is used in loading catalyst 92.9 gram dilutions, and the bed height is 410mm, and reaction raw materials is C
4Hydrocarbon mixture, it is preceding with 15～20%NaH to advance reactor
2PO
4Solution washing.The charging procatalyst heats up under nitrogen purging 245 ℃ and activates 3 hours, and five sampling resultses of reaction pressure 4.0MPa reaction end gas are: see Table 1.
Reaction conditions and result are:
The No temperature of reaction ℃ total alkene transformation efficiency of air speed LHSV hr liquid yield % %
1 135 4.28 40.95 48.94
2 135 3.85 46.25 55.93
3 145 3.84 46.12 57.14
4 155 3.84 51.23 64.71
5 171 3.85 56.11 72.44
The running 88 days in oil yield rate be 1793Kg gasoline/Kg catalyzer.Gasoline octane rating RON=98～99, acid-base reaction are neutral, and copper corrosion is qualified, and the product boiling range is:
Quantity of distillate % recovered temperature
Initial boiling point 42
10 90
50 113
90 180
Do 191
Total quantity of distillate % 96
Residual quantity % 1.0
Rate of loss % 3.0
Spent catalyst does not lump, and easily draws off degree of grinding＞10 orders, 82.24%, 10～20 orders, 3.73%,＜20 orders 11.96%, fine powder 2.08%.
Table 1
Component
Form the total alkene of the % methane propane Trimethylmethane normal butane anti-butylene maleic of n-butene iso-butylene
No
Raw material 0.51 0.15 24.62 15.99 18.85 21.53 13.88 4.47 58.88
1 0.30 27.53 21.66 9.55 0 26.99 13.98 50.51
2 0.56 0 28.93 22.31 7.59 0 26.53 14.02 48.14
3 0.59 0 29.82 22.77 6.50 0 26.46 13.73 46.70
4 0.63 0.11 32.14 24.50 4.49 0 24.90 13.02 42.41
5 0.74 0 35.53 26.74 3.96 0 21.32 11.60 36.88
6 0.72 0 36.27 27.44 4.04 0 20.18 11.30 35.52
Claims (9)
1, low temperature coincidence process process comprises:
A) in reactor, be reaction pressure 2.0～6.0mpa helping superimposed operational condition; 130～230 ℃ of temperature of reaction; Liquid air speed 2.5～5.0h
-1, the liquefied gas raw material being contacted with polymerization catalyst, thereby obtain product liquid and gaseous stream, said catalyzer is H
3PO
4/ activated-carbon catalyst, H wherein
3PO
4Content is 30～60%;
B) H
3PO
4/ activated-carbon catalyst is to be carrier dipping technical pure H with gac
3PO
4Form, and gac is a coal mass active carbon, requires in advance to handle with technical hydrochloric acid;
C) from above-mentioned gaseous stream, isolate the aforesaid liquid product;
D) above-mentioned product liquid is C
5-C
9Branched-chain alkene, i.e. polymer gasoline;
E) above-mentioned gas stream is recycled in the above-mentioned reactor.
2, low temperature coincidence process process according to claim 1, wherein said separating step (C) is by flash distillation and stable carrying out.
3, low temperature coincidence process process according to claim 1 is characterized in that the coal mass active carbon specific surface area is 700～1300m
2/ g, pore volume is 0.4～0.8ml/g.
4, low temperature coincidence process process according to claim 1, the concentration of hydrochloric acid that wherein said carrier gives processing is 1: 1,1: 4, or 1: 8 technical hydrochloric acid (concentrated hydrochloric acid: water).
5, low temperature coincidence process process according to claim 1, wherein said technical pure H
3PO
4Concentration be 8: 2(acid: water).
6, low temperature coincidence process process according to claim 1, wherein said H
3PO
4Immersion condition is reflux 2～8 hours.
7, low temperature coincidence process process according to claim 1, wherein said polymerization catalyst will give activation before reaction.
8, low temperature coincidence process process according to claim 1, wherein polymerization catalyst gives activation condition and is: the nitrogen medium air speed is 1000～2000h
-1, pressure is 2.5mpa, temperature is 200～250 ℃, gives activation 2～4 hours.
9, low temperature coincidence process process according to claim 1, wherein polymerization catalyst gives activation condition and is: the air dielectric air speed is 1000～1200h
-1; Pressure is 0～0.5mpa; Temperature is 200～250 ℃; Time is 2～4 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90107695 CN1021114C (en) | 1990-09-17 | 1990-09-17 | Phosphoric acid/active carbon catalyst and coincidence process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90107695 CN1021114C (en) | 1990-09-17 | 1990-09-17 | Phosphoric acid/active carbon catalyst and coincidence process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1049373A CN1049373A (en) | 1991-02-20 |
| CN1021114C true CN1021114C (en) | 1993-06-09 |
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ID=4880673
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 90107695 Expired - Lifetime CN1021114C (en) | 1990-09-17 | 1990-09-17 | Phosphoric acid/active carbon catalyst and coincidence process |
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| Country | Link |
|---|---|
| CN (1) | CN1021114C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1063741C (en) * | 1995-07-21 | 2001-03-28 | 中国石化兰州炼油化工总厂 | Method for recovery of petroleum acids from mixed extract of isopropyl alcohol-ammonia water |
| CN107652152B (en) * | 2017-10-24 | 2020-07-03 | 丹东明珠特种树脂有限公司 | Isobutylene polymerization preparation process |
| CN107754852A (en) * | 2017-10-24 | 2018-03-06 | 丹东明珠特种树脂有限公司 | The cationic ion-exchange resin modified catalyst and its method of modifying of isobutene building-up reactions |
| CN109433233B (en) * | 2018-09-25 | 2021-04-13 | 蚌埠知博自动化技术开发有限公司 | Catalyst for preparing isooctene by isobutene dimerization and preparation method thereof |
-
1990
- 1990-09-17 CN CN 90107695 patent/CN1021114C/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| CN1049373A (en) | 1991-02-20 |
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